Articles Comprising Water-Soluble Polyvinyl Alcohol Film with Plasticizer Blend and Related Methods

ABSTRACT

Disclosed herein are articles that include water-soluble films, where the water-soluble films include a polyvinyl alcohol (PVOH) polymer and a combination of at least three plasticizers. The combination of plasticizers includes dipropylene glycol as a first plasticizer, a sugar alcohol such as sorbitol as a second plasticizer, and a polyol such as glycerin as a third plasticizer. When the PVOH polymer and plasticizers are blended in particular proportions and/or selected with regard to various criteria related to physical and chemical film properties, the resulting water-soluble film formed from the PVOH resin blend exhibits beneficial combinations of aged tensile strength, aged melting transition delta elevation, aged adhesion value, and/or resistance to seal peeling, which provide strong film seals that retain their water-solubility characteristics.

FIELD OF THE DISCLOSURE

The disclosure relates generally to articles that include water-solublefilms and a household care composition proximal to the film, where thefilms include a polyvinyl alcohol (PVOH) resin and a blend ofplasticizers, and which can be used for contact with liquids, solids, orcombinations thereof. The disclosure further relates to methods ofmaking the films as well as articles, such as packets and pouches madefrom the films, which are optionally filled with active components,e.g., detergents, to make measured dose pouches. More particularly, thedisclosure relates to such films, articles, packets, and pouches withone or more benefits such as improved physical and chemical properties,in particular improved film seal strength, for end uses and/orresistance to change in solubility characteristics upon contact withchemicals, after sealing to form a packet, or both, together withsuitable processability.

BACKGROUND

Water-soluble polymeric films are commonly used as packaging materialsto simplify dispersing, pouring, dissolving and dosing of a material tobe delivered. For example, packets made from water-soluble film arecommonly used to package household care compositions, e.g., a pouchcontaining a laundry or dish detergent. A consumer can directly add thepouch to a mixing vessel, such as a bucket, sink or washing machine.Advantageously, this provides for accurate dosing while eliminating theneed for the consumer to measure the composition. The pouch may alsoreduce mess that would be associated with dispensing a similarcomposition from a vessel, such as pouring a liquid laundry detergentfrom a bottle. The pouch also insulates the composition therein fromcontact with the user's hands. In sum, soluble polymeric film packetscontaining pre-measured agents provide for convenience of consumer usein a variety of applications.

Some water-soluble polymeric films that are used to make articles suchas packets will incompletely dissolve during a wash cycle, leaving filmresidue on items within the wash. Such problems may particularly arisewhen the pouch is used under stressed wash conditions, such as when thepouch is used in cold water (e.g., water as low as 5° C. and/or up to10° C. or 15° C.), in a short wash cycle, and/or in a low-water washcycle (e.g., wash liquors from about 3 L to about 20 L). Notably,environmental concerns and energy cost are driving consumer desire forutilizing colder wash water and shorter wash cycles.

The formation of water-soluble single unit dose (SUD) articles mayinclude attachment of at least an upper layer of water soluble film to alower layer of water-soluble film. In the case of a multi-compartmentpouch, it is sometimes desirable to have one pouch compartment separatedfrom a second pouch compartment by a middle layer of water-soluble film,i.e. in so-called superposed multi-compartment pouches. In such asuperposed multi-compartment pouch there is a seal between the top filmand the middle film, and between the middle film and the bottom film. Inanother embodiment of a multi-compartment pouch, two pouch compartmentsare positioned side-by-side, for example including two layers ofwater-soluble film which are sealed in a middle region between pouchcompartments. In such side-by-side pouches, a good seal quality betweenadjacent compartments is desired to prevent liquid migration from onecompartment to the other through the seal. Such pouches known in the artdo not have seals as strong as desired. While it is possible to create astrong seal by heat sealing the layers together, this can lead toproblems such as weakness at the edge of the heat seal and leakingpouches. Additionally, heat sealing may induce additional crystallinity,resulting in seals that may be less soluble than a corresponding sealproduced by solution sealing.

There remains a need for water-soluble films and related articles suchas packets having the desired characteristics of good water solubility(e.g., cold water solubility), chemical resistance, chemical andphysical compatibility with laundry actives, other detergent actives, orother compositions in contact with the film or pouch formed therefrom,and desirable mechanical properties including strong seals, high tensilestrength, and good processability. Once formed, whether as a film or acomposition-containing pouch formed therefrom, supply chainconsiderations can result in a substantial passage of time (e.g., atnormal or elevated temperatures) before utilization of the end product.Accordingly, there is further a need for improved mechanical properties(e.g., seal strength, tensile strength) after such passage of time andchange in film properties.

SUMMARY

The disclosure relates to articles that include a water-soluble film anda household care composition proximal to the film, where thewater-soluble film includes a polyvinyl alcohol (PVOH) polymer (e.g.,one or more PVOH homopolymers, one or more PVOH copolymers, andcombinations thereof) and a combination of at least three plasticizers.The combination of plasticizers includes dipropylene glycol as a firstplasticizer, a sugar alcohol (e.g. sorbitol) as a second plasticizer,and a polyol (e.g. glycerin) as a third plasticizer. When the PVOHpolymer(s) and plasticizers are blended in particular proportions and/orselected with regard to various criteria related to physical andchemical film properties, the resulting water-soluble film formed fromthe PVOH resin exhibits a beneficial combination (e.g., two, three, orfour of) of aged tensile strength, aged melting transition deltaelevation, aged adhesion value, and/or resistance to seal peeling. Suchcombinations of properties provide the ability to form film seals thatare strong and that retain their water-solubility characteristics, forexample including film-film seals that are formed without heat sealing(e.g., by solvent welding or solvent sealing and/or without applicationof heat).

The present disclosure also relates to an article that includes awater-soluble film and a household care composition proximal to thefilm, where the film includes a polyvinyl alcohol (PVOH) polymer;dipropylene glycol as a first plasticizer; a sugar alcohol as a secondplasticizer; and a polyol as a third plasticizer, the third plasticizerbeing different from the first plasticizer and the second plasticizer.In a refinement, the water-soluble film includes: the polyvinyl alcohol(PVOH) polymer; dipropylene glycol as the first plasticizer; sorbitol asthe second plasticizer; and glycerin as the third plasticizer; whereinthe first, second, and third plasticizers are present in thewater-soluble film in a combined amount in a range of about 5 parts toabout 50 parts total plasticizer per 100 parts total resin (phr) in thewater-soluble film. In another refinement, the first plasticizer ispresent in the water-soluble film in an amount in a range of about 10wt. % to about 65 wt. % relative to the combined amount of the first,second, and third plasticizers in the water-soluble film. In anotherrefinement, the second plasticizer is present in the water-soluble filmin an amount in a range of about 10 wt. % to about 65 wt. % relative tothe combined amount of the first, second, and third plasticizers in thewater-soluble film. In another refinement, the third plasticizer ispresent in the water-soluble film in an amount in a range of about 25wt. % to about 80 wt. % relative to the combined amount of the first,second, and third plasticizers in the water-soluble film.

The present disclosure also relates to an article including awater-soluble film of any of the various disclosed embodiments and ahousehold care composition proximal to the film, where the articleincludes a first surface of said film solvent-sealed to a second surfaceof the same film or to a surface of a second film of any of the variousdisclosed embodiments.

The present disclosure also relates to an article including awater-soluble film of any of the various disclosed embodiments in theform of a pouch defining an interior pouch volume (e.g., furthercomprising a composition contained in the interior pouch volume).

The present disclosure also relates to a method of forming the articlesdescribed herein, where the method includes the steps of: providing thewater-soluble film, where the film defines an interior pouch containervolume; filling the container volume with a household care composition;and sealing the film to form a sealed compartment, wherein the sealedcompartment contains the composition.

The present disclosure also relates to a method of treating a substrate,where the method includes the step of contacting the substrate with anarticle as described herein.

The present disclosure relates to a method for making an articlecomprising a water-soluble film and a household care compositionproximal to the film, the method including: selecting a polyvinylalcohol (PVOH) polymer, a first plasticizer, a second plasticizer, and athird plasticizer; selecting a desired range for at least a first filmproperty and a second film property; forming a plurality ofwater-soluble films comprising the PVOH polymer, the first plasticizer,the second plasticizer, and the third plasticizer at differentconcentrations of the PVOH polymer, the first plasticizer, the secondplasticizer, and the third plasticizer, wherein at least one of thewater-soluble films has a film property within the desired range foreach of the first and second film properties; determining the first andsecond film properties for each of the formed water-soluble films;identifying a film concentration for each of the PVOH polymer, the firstplasticizer, the second plasticizer, and the third plasticizer from theformed plurality of water-soluble films, the identified filmconcentration having a first film property and a second film propertywithin the desired range for each property; and forming a filmcomprising the PVOH polymer, the first plasticizer, the secondplasticizer, and the third plasticizer at the identified filmconcentration.

The present disclosure also relates to use of dipropylene glycol as aplasticizer for a water-soluble polyvinyl alcohol film, in combinationwith a sugar alcohol plasticizer and a polyol plasticizer, for improvingone or more of (a) aged melting transition delta elevation of the filmas measured by the Aged Melting Transition Delta Test; (b) aged adhesionvalue of the film as measured by the Aged Adhesion Test; and (c) agedtensile strength of the film as measured by the Aged Tensile StrengthTest.

In a particular refinement of the various embodiments, the water-solublefilm has at least two of the three properties (a), (b), and (c): (a) anaged melting transition delta elevation of about 12° C. or less asmeasured by the Aged Melting Transition Delta Test; (b) an aged adhesionvalue of at least about 1300 g/s as measured by the Aged Adhesion Test;and (c) an aged tensile strength of at least about 25 MPa as measured bythe Aged Tensile Strength Test. In another refinement, the water-solublefilm has at least two of the three properties (a), (b), and (c): (a) anaged melting transition delta elevation of about 11° C. or less asmeasured by the Aged Melting Transition Delta Test; (b) an aged adhesionvalue of at least about 1900 g/s as measured by the Aged Adhesion Test;and (c) an aged tensile strength of at least about 30 MPa as measured bythe Aged Tensile Strength Test. In another refinement, the water-solublefilm has at least two of the three properties (a), (b), and (c): (a) anaged melting transition delta elevation of about 11° C. or less asmeasured by the Aged Melting Transition Delta Test; (b) an aged adhesionvalue of at least about 2500 g/s as measured by the Aged Adhesion Test;and (c) an aged tensile strength of at least about 32.5 MPa as measuredby the Aged Tensile Strength Test.

For the articles, compositions and methods described herein, optionalfeatures, including but not limited to components, compositional rangesthereof, substituents, conditions, and steps, are contemplated to beselected from the various aspects, embodiments, and examples providedherein.

Further aspects and advantages will be apparent to those of ordinaryskill in the art from a review of the following detailed description andaccompanying drawings. While the compositions and methods aresusceptible of embodiments in various forms, the description hereafterincludes specific embodiments with the understanding that the disclosureis illustrative, and is not intended to limit the invention to thespecific embodiments described herein.

DESCRIPTION OF THE DRAWINGS

The following detailed description of the various disclosed methods,processes, compositions, and articles refers to the accompanyingdrawings in which:

FIG. 1 is a side cross-sectional view of a water-soluble pouch articleincluding a composition contained therein.

FIG. 2 is a graph illustrating Aged Tensile Strength values as afunction of molar volume for PVOH films according to the disclosureincorporating a blend of different plasticizers including glycerin,sorbitol, and an additional plasticizer.

FIG. 3 is a graph illustrating Sum Seal Tear values as a function ofmolar volume for PVOH films according to the disclosure incorporating ablend of different plasticizers including glycerin, sorbitol, and anadditional plasticizer.

FIGS. 4A-4C are a series of simplex contour plots illustrating AgedMelting Transition Delta values (i.e., difference in melting transitionvalue upon film aging), Aged Adhesion values, and Aged Tensile Strengthvalues for a PVOH copolymer blend film according to the disclosureincorporating a blend of different plasticizers ratios includingdipropylene glycol, sorbitol, and glycerin at different totalplasticizer loadings (4A: 44.4 phr plasticizer loading, 4B: 37.0 phrplasticizer loading, 4C: 29.6 phr plasticizer loading).

FIG. 5 is a simplex plot illustrating plasticizer compositions meeting afirst combination of selected Aged Melting Transition Delta values, AgedAdhesion values, and Aged Tensile Strength values for a PVOH copolymerblend film according to the disclosure incorporating a blend ofdifferent plasticizers including dipropylene glycol, sorbitol, andglycerin at a 29.6 phr (parts per hundred parts resin, in this case PVOHresin) plasticizer loading.

FIG. 6 is a simplex plot illustrating plasticizer compositions meeting asecond combination of selected Aged Melting Transition Delta values,Aged Adhesion values, and Aged Tensile Strength values for a PVOHcopolymer blend film according to the disclosure incorporating a blendof different plasticizers including dipropylene glycol, sorbitol, andglycerin at a 29.6 phr plasticizer loading.

FIG. 7 is a simplex plot illustrating plasticizer compositions meeting athird combination of selected Aged Melting Transition Delta values, AgedAdhesion values, and Aged Tensile Strength values for a PVOH copolymerblend film according to the disclosure incorporating a blend ofdifferent plasticizers including dipropylene glycol, sorbitol, andglycerin at a 29.6 phr plasticizer loading.

FIG. 8 is a simplex plot illustrating plasticizer compositions meeting afirst combination of selected Aged Melting Transition Delta values, AgedAdhesion values, and Aged Tensile Strength values for a PVOH copolymerblend film according to the disclosure incorporating a blend ofdifferent plasticizers including dipropylene glycol, sorbitol, andglycerin at a 37.0 phr plasticizer loading.

FIG. 9 includes graphs showing Aged Melting Transition Delta values andAged Tensile Strength values for PVOH copolymer blend films according tothe disclosure incorporating a blend of different plasticizers includingdipropylene glycol, sorbitol, and glycerin at a 37.0 phr plasticizerloading.

FIG. 10 includes a graph showing Sum Seal Tears values for PVOHcopolymer blend films according to the disclosure incorporating a blendof different plasticizers including dipropylene glycol, sorbitol, andglycerin at a 37.0 phr plasticizer loading.

DETAILED DESCRIPTION

Disclosed herein are articles that include water-soluble films andhousehold care compositions proximal to the films, where thewater-soluble films include a polyvinyl alcohol polymer and blends ofplasticizers including at least dipropylene glycol and one additionalplasticizer as described herein, and delivery pouches formed from orotherwise including the films.

Some water-soluble polymeric films that are used to make articles suchas packets will incompletely dissolve in water during normal use, forexample during a laundry wash cycle for packets containing alaundry-related composition (e.g., thereby leaving film residue on itemswithin the wash).

Water-soluble polymeric films based on PVOH can be subject to changes insolubility characteristics. The acetate group in the co-poly(vinylacetate vinyl alcohol) polymer is known by those skilled in the art tobe hydrolysable by either acid or alkaline hydrolysis. As the degree ofhydrolysis increases, a polymer composition made from the PVOHhomopolymer resin will have increased mechanical strength but reducedsolubility at lower temperatures (e.g., requiring hot water temperaturesfor complete dissolution). Accordingly, exposure of a PVOH homopolymerresin to an alkaline environment (e.g., resulting from a laundrybleaching additive) can transform the resin from one which dissolvesrapidly and entirely in a given aqueous environment (e.g., a cold watermedium) to one which dissolves slowly and/or incompletely in the aqueousenvironment, potentially resulting in undissolved polymeric residue atthe end of a wash cycle. This is an inherent weakness in the applicationof films based on just the vinyl acetate/alcohol co-polymer typified bycommercial PVOH homopolymer resins.

PVOH copolymer resins with pendant carboxyl groups, such as vinylalcohol/hydrolyzed methyl acrylate sodium salt resins, can form lactonerings between neighboring pendant carboxyl and alcohol groups, thusreducing the water solubility of the PVOH copolymer resin. In thepresence of a strong base such as a laundry bleaching additive, thelactone rings can open over the course of several weeks at relativelywarm (ambient) and high humidity conditions (e.g., via lactonering-opening reactions to form the corresponding pendant carboxyl andalcohol groups with increased water solubility). Thus, contrary to theeffect observed with PVOH homopolymer films, it is believed that such aPVOH copolymer film can become more soluble due to chemical interactionsbetween the film and an alkaline composition inside the pouch duringstorage. Consequently, as they age, the packets may become increasinglyprone to premature dissolution during a hot wash cycle (nominally 40°C.), and may in turn decrease the efficacy of certain laundry activesdue to the presence of the bleaching agent and the resulting pHinfluence.

In formulating a suitable film for a given application (e.g., acomposition-in-pouch article for a washing operation), multiple factorsmust be taken in to account, in particular when forming a film-film sealthat both is strong and retains its water solubility characteristics.These factors include: (1) aged tensile strength, where a higher agedtensile strength represents stronger pouches in general and strongerpouch seals when the film is the limiting or weakest element of a seal;(2) aged melting transition delta elevation, where a lower melting pointelevation upon aging represents prevention of crystalline growth regions(which weaken a seal) and maintenance of amorphous polymer regions(which strengthen a seal); (3) aged adhesion value, where a higheradhesion value is favorable and is representative of seal strength; and(4) a resistance to seal peeling or delamination, where a tendency of aseal to tear instead of peel when a pulling force is applied to the sealrepresents a high seal strength (e.g., where film mechanical strength isthe limiting factor instead of seal strength). Often, water-solublepolymer resins, whether PVOH or otherwise, may have suitablecharacteristics with respect to some of these factors, but they can havepoor characteristics with respect to other of these factors.Accordingly, it would be desirable to provide a water-soluble film inwhich many, if not all, of these factors have favorable properties inthe film, in particular where favorable properties as characterized bythe various aging tests at elevated temperatures herein can berepresentative of similarly favorable properties for films after longerstorage times at lower temperatures during actual use.

Accounting for these factors, the present disclosure includes articlesthat include a water-soluble film and a household care compositionproximal to the film, where the water-soluble film includes a polyvinylalcohol (PVOH) polymer and a combination of at least three plasticizers.A plasticizer is a liquid, solid, or semi-solid that is added to amaterial (usually a resin or elastomer) making that material softer,more flexible (by decreasing the glass-transition temperature of thepolymer), and easier to process. A polymer can be internally plasticizedby chemically modifying the polymer or monomer. In addition or in thealternative, a polymer can be externally plasticized by the addition ofa suitable plasticizing agent. The combination of plasticizers for thefilm described herein includes dipropylene glycol as a firstplasticizer, a sugar alcohol as a second plasticizer, and a polyol as athird plasticizer which is different from the first plasticizer and thesecond plasticizer. In one type of embodiment, the water-soluble filmwill be substantially free from plasticizers other than the than thefirst, second, and third plasticizers (e.g., completely free from otherplasticizers, or less than about 1 phr of other plasticizers, or lessthan about 0.5 phr of other plasticizers, or less than about 0.2 phr ofother plasticizers). In other embodiments, the water-soluble film caninclude further plasticizers (e.g., sugar alcohols, polyols, orotherwise) other than the first, second, and third plasticizers. Thefilm optionally can include one or more additional components includingfillers, surfactants, and other additives as is known in the art forPVOH films, and as described in more detail below. The sugar alcoholplasticizer can be isomalt, maltitol, sorbitol, xylitol, erythritol,adonitol, dulcitol, pentaerythritol, or mannitol, for example. In aparticular aspect, the sugar alcohol plasticizer can be sorbitol or asorbitol-containing plasticizer such as isomalt. The polyol plasticizercan be glycerin, diglycerin, ethylene glycol, diethylene glycol,triethyleneglycol, tetraethylene glycol, a polyethylene glycol up to 400MW, neopentyl glycol, propylene glycol, 1,3-propanediol,2-methyl-1,3-propanediol, trimethylolpropane, or a polyether polyol, forexample. In a particular aspect, the polyol plasticizer can be glycerin,propylene glycol, or 1,3-propanediol, for example glycerin. In one classof embodiments, the water-soluble film includes the polyvinyl alcohol(PVOH) polymer and a plasticizer blend including dipropylene glycol asthe first plasticizer, sorbitol as the second plasticizer, and glycerinas the third plasticizer.

The water-soluble film can include at least one plasticizer (e.g., asthe second plasticizer, the third plasticizer, or otherwise) which isgenerally solid at room temperature and/or common use, storage, ortransportation temperatures, for example a plasticizer which is solid ina range of about 10° C. or 20° C. to about 30° C., 40° C., or 50° C.and/or has a melting point above such range (e.g., a melting point belowcommon film-formation process temperature such as casting, but abovecommon use, storage, or transportation temperatures). Examples of suchsolid plasticizers include sorbitol (95° C. melting point) andtrimethylolpropane (58° C. melting point). Additionally oralternatively, the water-soluble film can include at least oneplasticizer (e.g., as the second plasticizer, the third plasticizer, orotherwise) which is generally liquid at room temperature and/or commonuse, storage, or transportation temperatures, for example which isliquid in a range of about 10° C. or 20° C. to about 30° C., 40° C., or50° C. and/or has a melting point below such range.

The first, second, and third plasticizers can be present in thewater-soluble film in a combined amount in a range of about 5 parts toabout 50 parts total plasticizer per 100 parts total resin (phr) in thewater-soluble film. In some embodiments, the three plasticizers can bepresent in the water-soluble film in a combined amount in a range ofabout 5 phr to about 40 phr, for example about 10 phr, 15 phr or 30 phrto about 40 phr, about 10 phr or 15 phr to about 30 phr or 35 phr, orabout 20 phr or 25 phr to about 35 phr. The three plasticizers can bepresent in any desired relative amount to each other. In variousaspects, each of the first, second, and/or third plasticizerindividually can be present in the water-soluble film in an amount in arange of about 10 wt. % to about 80 wt. % relative to the combinedamount of the first, second, and third plasticizers in the water-solublefilm. In an aspect, the first plasticizer is present in thewater-soluble film in an amount in a range of about 10 wt. % to about 65wt. % relative to the combined amount of the first, second, and thirdplasticizers in the water-soluble film (e.g., at least about 10, 15, or20 wt. % and/or up to about 20, 30, 40, 50, or 65 wt. %). In anotheraspect, the second plasticizer is present in the water-soluble film inan amount in a range of about 10 wt. % to about 65 wt. % relative to thecombined amount of the first, second, and third plasticizers in thewater-soluble film (e.g., e.g., at least about 10, 15, or 20 wt. %and/or up to about 20, 30, 40, 50, or 65 wt. %). In another aspect, thethird plasticizer is present in the water-soluble film in an amount in arange of about 25 wt. % to about 80 wt. % relative to the combinedamount of the first, second, and third plasticizers in the water-solublefilm (e.g., at least about 25, 30, 35, or 40 wt. % and/or up to about50, 60, 70, 75, or 80 wt. %).

Various particular concentration combinations of the first dipropyleneglycol plasticizer, the second plasticizer (e.g., sorbitol orotherwise), and the third plasticizer (e.g., glycerin or otherwise) arecontemplated.

The first plasticizer may be present in the water-soluble film in anamount in a range of about 10 wt. % to about 40 wt. % (e.g., about 20wt. % to 40 wt. %), the second plasticizer is present in thewater-soluble film in an amount in a range of about 10 wt. % to about 30wt. % (e.g., about 10 wt. % to 30 wt. %), and the third plasticizer ispresent in the water-soluble film in an amount in a range of about 40wt. % to about 70 wt. % (e.g., about 50 wt. % to 60 wt. %), where eachweight concentration is relative to the combined amount of the first,second, and third plasticizers in the water-soluble film. In these typesof embodiments, the three plasticizers can be present in thewater-soluble film in a combined amount in a range of about 25 phr toabout 40 phr or 45 phr. Films according to these types of embodimentsoptionally can have an aged tensile strength of at least about 25 MPa or30 MPa as measured by the Aged Tensile Strength Test (e.g., up to about30, 35, 38, 40, 45, or 50 MPa). Alternatively or additionally, the filmscan have a seal tear value of at least about 170% as measured by the SumSeal Tear Test (e.g., up to about 180% or 200%).

The first plasticizer may be present in the water-soluble film in anamount in a range of about 13 wt. % to about 46 wt. %, the secondplasticizer is present in the water-soluble film in an amount in a rangeof about 13 wt. % to about 58 wt. %, and the third plasticizer ispresent in the water-soluble film in an amount in a range of about 28wt. % to about 73 wt. % relative to the combined amount of the first,second, and third plasticizers in the water-soluble film, wherein eachweight concentration is relative to the combined amount of the first,second, and third plasticizers in the water-soluble film. In these typesof embodiments, the three plasticizers optionally can be present in thewater-soluble film in a combined amount in a range of about 25 phr or 30phr to about 40 phr or 45 phr.

The first plasticizer may be present in the water-soluble film in anamount in a range of about 13 wt. % to about 38 wt. %, the secondplasticizer is present in the water-soluble film in an amount in a rangeof about 16 wt. % to about 58 wt. %, and the third plasticizer ispresent in the water-soluble film in an amount in a range of about 28wt. % to about 71 wt. %, wherein each weight concentration is relativeto the combined amount of the first, second, and third plasticizers inthe water-soluble film. In these types of embodiments, the threeplasticizers optionally can be present in the water-soluble film in acombined amount in a range of about 25 phr or 30 phr to about 40 phr or45 phr.

The first plasticizer may be present in the water-soluble film in anamount in a range of about 13 wt. % to about 58 wt. %, the secondplasticizer is present in the water-soluble film in an amount in a rangeof about 13 wt. % to about 58 wt. %, and the third plasticizer ispresent in the water-soluble film in an amount in a range of about 28wt. % to about 73 wt. %, wherein each weight concentration is relativeto the combined amount of the first, second, and third plasticizers inthe water-soluble film. In these types of embodiments, the threeplasticizers optionally can be present in the water-soluble film in acombined amount in a range of about 20 phr or 25 phr to about 30 phr or35 phr.

The first plasticizer may be present in the water-soluble film in anamount in a range of about 13 wt. % to about 50 wt. %, the secondplasticizer is present in the water-soluble film in an amount in a rangeof about 13 wt. % to about 50 wt. %, and the third plasticizer ispresent in the water-soluble film in an amount in a range of about 36wt. % to about 73 wt. %, wherein each weight concentration is relativeto the combined amount of the first, second, and third plasticizers inthe water-soluble film. In these types of embodiments, the threeplasticizers optionally can be present in the water-soluble film in acombined amount in a range of about 20 phr or 25 phr to about 30 phr or35 phr.

The first plasticizer may be present in the water-soluble film in anamount in a range of about 13 wt. % to about 45 wt. %, the secondplasticizer is present in the water-soluble film in an amount in a rangeof about 19 wt. % to about 52 wt. %, and the third plasticizer ispresent in the water-soluble film in an amount in a range of about 35wt. % to about 65 wt. %, wherein each weight concentration is relativeto the combined amount of the first, second, and third plasticizers inthe water-soluble film. In these types of embodiments, the threeplasticizers optionally can be present in the water-soluble film in acombined amount in a range of about 20 phr or 25 phr to about 30 phr or35 phr.

The first plasticizer may be present in the water-soluble film in anamount in a range of about 13 wt. % to about 39 wt. %, the secondplasticizer is present in the water-soluble film in an amount in a rangeof about 22 wt. % to about 38 wt. %, and the third plasticizer ispresent in the water-soluble film in an amount in a range of about 39wt. % to about 64 wt. %, wherein each weight concentration is relativeto the combined amount of the first, second, and third plasticizers inthe water-soluble film. In these types of embodiments, the threeplasticizers optionally can be present in the water-soluble film in acombined amount in a range of about 20 phr or 25 phr to about 30 phr or35 phr.

The first plasticizer may be present in the water-soluble film in anamount in a range of about 13 wt. % to about 19 wt. %, the secondplasticizer is present in the water-soluble film in an amount in a rangeof about 41 wt. % to about 52 wt. %, and the third plasticizer ispresent in the water-soluble film in an amount in a range of about 35wt. % to about 44 wt. %, wherein each weight concentration is relativeto the combined amount of the first, second, and third plasticizers inthe water-soluble film. In these types of embodiments, the threeplasticizers optionally can be present in the water-soluble film in acombined amount in a range of about 20 phr or 25 phr to about 30 phr or35 phr.

Various particular aged property combinations of the water-soluble filmare contemplated.

The water-soluble film may have at least two of the three properties(a), (b), and (c): (a) an aged melting transition delta elevation ofabout 12° C. or less as measured by the Aged Melting Transition DeltaTest (e.g., about 0, 2, or 4° C. to about 12° C.); (b) an aged adhesionvalue of at least about 1300 g/s as measured by the Aged Adhesion Test;and (c) an aged tensile strength of at least about 25 MPa as measured bythe Aged Tensile Strength Test (e.g., up to about 30, 35, 38, 40, 45, or50 MPa). In one type of embodiment, the film will have properties (a)and (b). In another type of embodiment, the film will have properties(a) and (c). In another type of embodiment, the film will haveproperties (b) and (c). In another type of embodiment, the film willhave all three properties (a), (b), and (c).

The water-soluble film may have at least two of the three properties(a), (b), and (c): (a) an aged melting transition delta elevation ofabout 11° C. or less as measured by the Aged Melting Transition DeltaTest (e.g., about 0, 2, or 4° C. to about 11° C.); (b) an aged adhesionvalue of at least about 1900 g/s as measured by the Aged Adhesion Test;and (c) an aged tensile strength of at least about 30 MPa as measured bythe Aged Tensile Strength Test (e.g., up to about 35, 38, 40, 45, or 50MPa). In one type of embodiment, the film will have properties (a) and(b). In another type of embodiment, the film will have properties (a)and (c). In another type of embodiment, the film will have properties(b) and (c). In another type of embodiment, the film will have all threeproperties (a), (b), and (c).

The water-soluble film may have at least two of the three properties(a), (b), and (c): (a) an aged melting transition delta elevation ofabout 11° C. or less as measured by the Aged Melting Transition DeltaTest (e.g., about 0, 2, or 4° C. to about 11° C.); (b) an aged adhesionvalue of at least about 2500 g/s as measured by the Aged Adhesion Test;and (c) an aged tensile strength of at least about 32.5 MPa as measuredby the Aged Tensile Strength Test (e.g., up to about 35, 38, 40, 45, or50 MPa). In one type of embodiment, the film will have properties (a)and (b). In another type of embodiment, the film will have properties(a) and (c). In another type of embodiment, the film will haveproperties (b) and (c). In another type of embodiment, the film willhave all three properties (a), (b), and (c).

The PVOH polymer of the water-soluble film is not particularly limitedand it can include a single PVOH homopolymer, a single PVOH copolymer,or a blend of PVOH homopolymers, copolymers, or combinations thereof. Insome aspects, the water-soluble film can include a water-soluble polymerwhich is other than a PVOH polymer. In one class of embodiments, thePVOH polymer will be a partially or fully hydrolyzed PVOH homopolymerincluding vinyl alcohol monomer units and optionally vinyl acetatemonomer units. In another type of embodiment, the PVOH polymer will be apartially or fully hydrolyzed PVOH copolymer including an anionicmonomer unit, a vinyl alcohol monomer unit, and optionally a vinylacetate monomer unit. In various embodiments, the anionic monomer can beone or more of vinyl acetic acid, maleic acid, monoalkyl maleate,dialkyl maleate, monomethyl maleate, dimethyl maleate, maleicanyhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate,monomethyl fumarate, dimethyl fumarate, fumaric anyhydride, itaconicacid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride,vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid,2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts of the foregoing (e.g., sodium, potassium, or otheralkali metal salts), esters of the foregoing (e.g., methyl, ethyl, orother C₁-C₄ or C₆ alkyl esters), and combinations thereof (e.g.,multiple types of anionic monomers or equivalent forms of the sameanionic monomer). For example, the anionic monomer can include one ormore acrylamido methylpropanesulfonic acids (e.g.,2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid) and alkali metal saltsthereof (e.g., sodium salts). Similarly, the anionic monomer can includeone or more of monomethyl maleate and alkali metal salts thereof (e.g.,sodium salts). Examples of non-PVOH water-soluble polymers includepolyethyleneimines, polyvinyl pyrrolidones, polyalkylene oxides,polyacrylamides, cellulose ethers, cellulose esters, cellulose amides,polyvinyl acetates, polyamides, gelatines, methylcelluloses,carboxymethylcelluloses and salts thereof, dextrins, ethylcelluloses,hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins,starches, modified starches, guar gum, gum Acacia, xanthan gum,carrageenan, and polyacrylates and salts thereof.

As noted, the PVOH polymer can include blends of PVOH polymers, forexample a blend including two or more different PVOH homopolymers, ablend including two or more different PVOH copolymers, or a blendincluding at least one PVOH homopolymer and at least one PVOH copolymer.In a particular PVOH copolymer blend embodiment, the blend includes afirst PVOH copolymer including a first anionic monomer unit, and asecond PVOH copolymer including a second anionic monomer unit differentfrom the first anionic monomer unit. For example, the first anionicmonomer can include one or more acrylamido methylpropanesulfonic acidsand alkali metal salts thereof, and the second anionic monomer caninclude one or more of monomethyl maleate and alkali metal saltsthereof. The first PVOH copolymer can be present in an amount in a rangeof about 10 wt. % to about 80 wt. % (e.g., 10 wt. % to 60 wt. %, 40 wt.% to 60 wt. %, 10 wt. % to 30 wt. %) of total PVOH polymers in the film,and the second PVOH copolymer can be present in an amount in a range ofabout 20 wt. % to about 90 wt. % (e.g., 40 wt. % to 90 wt. %, 40 wt. %to 60 wt. %, 70 wt. % to 90 wt. %) of total PVOH polymers in the film.

In an aspect, the disclosure relates to a method for making awater-soluble film including a selected PVOH polymer and three or moreplasticizers, for example a first plasticizer (e.g., dipropyleneglycol), a second plasticizer (e.g., a sugar alcohol such as sorbitol),and a third plasticizer (e.g., a polyol such as glycerin). In additionto the resin and plasticizer components, desired ranges for at least afirst film property and a second film property can be achieved by theteachings herein (e.g., properties such as aged melting transition deltaelevation, aged adhesion value, aged adhesion value, and seal tearvalue). The desired ranges can reflect upper desired boundaries, lowerdesired boundaries, or a span between lower and upper desiredboundaries. Additional film properties beyond the first and second(e.g., third film property, fourth film property, etc.) can beconsidered when making the film. A plurality of water-soluble filmsincluding the PVOH polymer, the first plasticizer, the secondplasticizer, and the third plasticizer at different concentrations forone or more of the PVOH polymer, the first plasticizer, the secondplasticizer, and the third plasticizer are then formed (e.g., whichfurther include any other film additives at consistent levels). Asillustrated in Example 4, the plurality of water-soluble films caninclude at least four different films at a given total plasticizerloading (e.g., three film formulations at vertices of a simplex regionfor the plasticizer composition and at least one film formulation at aninterior location of the simplex region). At least one of thewater-soluble films will have a film property within the desired rangefor each of the first and second film properties (e.g., throughiteration of formulation variations within the scope of the teachingsherein, if necessary). In an aspect, at least one of the water-solublefilms also will have a film property outside the desired range for eachof the first and second film properties (e.g., to facilitateinterpolation of boundaries between desired and undesired compositionproperties, for example to generate a contour map for the property). Foreach of the plurality of water-soluble films, the first and second filmproperties (e.g., and third, fourth, etc. film properties whenapplicable) are then determined for each of the formed water-solublefilms, for example by any suitable analytical technique. Afterdetermining the relevant properties for each film, a film concentrationis identified for each of the PVOH polymer, the first plasticizer, thesecond plasticizer, and the third plasticizer from the formed pluralityof water-soluble films, such that the identified film concentration hasa first film property and a second film property (e.g., and third,fourth, etc. film properties when applicable) within the desired rangefor each property. For example, interpolation or curve-fitting of thefilm properties of the tested films can be used to generate a map (e.g.,a 2D simplex map for a 3-plasticizer system with a fixed level ofplasticizer relative to PVOH resin) or other property-film concentrationrelationship for film concentration selection. A film including the PVOHpolymer, the first plasticizer, the second plasticizer, and the thirdplasticizer at the identified film concentration (e.g., in addition toany other film additives used when making the plurality of films) isthen formed using any suitable technique (e.g., solution casting, etc.).

The disclosed water-soluble films, articles such as delivery pouchesthat include the films, and related methods are contemplated to includeembodiments including any combination of one or more of the additionaloptional elements, features, and steps further described below(including those shown in the figures and examples), unless statedotherwise.

In any embodiment, the article, such as a water-soluble pouch, cancontain a composition. The composition is typically a household carecomposition. The composition can be selected from a liquid, solid orcombination thereof. As used herein, “liquid” includes free-flowingliquids, as well as pastes, gels, foams and mousses. Non-limitingexamples of liquids include light duty and heavy duty liquid detergentcompositions, fabric enhancers, detergent gels commonly used forlaundry, bleach and laundry additives. Gases, e.g., suspended bubbles,or solids, e.g. particles, may be included within the liquids. A “solid”as used herein includes, but is not limited to, powders, agglomerates,and mixtures thereof. Non-limiting examples of solids include: granules,micro-capsules, beads, noodles, and pearlized balls. Solid compositionsmay provide a technical benefit including, but not limited to,through-the-wash benefits, pre-treatment benefits, and/or aestheticeffects.

In any of the laundry-centric embodiments, the composition may beselected from the group of liquid light duty and liquid heavy dutyliquid detergent compositions, powdered detergent compositions, fabricenhancers, detergent gels commonly used for laundry, and bleach (e.g.,organic or inorganic bleach) and laundry additives, for example.

As used herein, the term “homopolymer” generally includes polymershaving a single type of monomeric repeating unit (e.g., a polymericchain consisting of or consisting essentially of a single monomericrepeating unit). For the particular case of PVOH, the term “homopolymer”(or “PVOH homopolymer”) further includes copolymers having adistribution of vinyl alcohol monomer units and vinyl acetate monomerunits, depending on the degree of hydrolysis (e.g., a polymeric chainconsisting of or consisting essentially of vinyl alcohol and vinylacetate monomer units). In the limiting case of 100% hydrolysis, a PVOHhomopolymer can include a true homopolymer having only vinyl alcoholunits.

As used herein, the term “copolymer” generally includes polymers havingtwo or more types of monomeric repeating units (e.g., a polymeric chainconsisting of or consisting essentially of two or more differentmonomeric repeating units, whether as random copolymers, blockcopolymers, etc.). For the particular case of PVOH, the term “copolymer”(or “PVOH copolymer”) further includes copolymers having a distributionof vinyl alcohol monomer units and vinyl acetate monomer units,depending on the degree of hydrolysis, as well as at least one othertype of monomeric repeating unit (e.g., a ter- (or higher) polymericchain consisting of or consisting essentially of vinyl alcohol monomerunits, vinyl acetate monomer units, and one or more other monomer units,for example anionic monomer units or alkylene (such as ethylene) monomerunits). In the limiting case of 100% hydrolysis, a PVOH copolymer caninclude a copolymer having vinyl alcohol units and one or more othermonomer units, but no vinyl acetate units.

As used herein, the term “comprising” indicates the potential inclusionof other agents, elements, steps, or features, in addition to thosespecified.

As used herein and unless specified otherwise, the terms “wt. %” and “wt%” are intended to refer to the composition of the identified element in“dry” (non water) parts by weight of the entire film (when applicable)or parts by weight of the entire composition enclosed within a pouch(when applicable). As used herein and unless specified otherwise, theterm “phr” is intended to refer to the composition of the identifiedelement in parts per one hundred parts water-soluble polymer (or resin;whether PVOH or otherwise) in the water-soluble film.

All ranges set forth herein include all possible subsets of ranges andany combinations of such subset ranges. By default, ranges are inclusiveof the stated endpoints, unless stated otherwise. Where a range ofvalues is provided, it is understood that each intervening value betweenthe upper and lower limit of that range and any other stated orintervening value in that stated range, is encompassed within thedisclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges, and are alsoencompassed within the disclosure, subject to any specifically excludedlimit in the stated range. Where the stated range includes one or bothof the limits, ranges excluding either or both of those included limitsare also contemplated to be part of the disclosure.

Water-Soluble Film Compositions

Water-soluble film compositions, optional ingredients for use therein,and methods of making the same are well known in the art, whether beingused for making relatively thin water-soluble films (e.g., as pouchmaterials) or otherwise.

In one class of embodiments, the water-soluble film includes polyvinylalcohol (PVOH), including homopolymers thereof (e.g., includingsubstantially only vinyl alcohol and vinyl acetate monomer units),copolymers thereof (e.g., including one or more other monomer units inaddition to vinyl alcohol and vinyl acetate units), and mixturesthereof. PVOH is a synthetic resin generally prepared by thealcoholysis, usually termed hydrolysis or saponification, of polyvinylacetate. Fully hydrolyzed PVOH, wherein virtually all the acetate groupshave been converted to alcohol groups, is a strongly hydrogen-bonded,highly crystalline polymer which dissolves only in hot water—greaterthan about 140° F. (60° C.). If a sufficient number of acetate groupsare allowed to remain after the hydrolysis of polyvinyl acetate, thePVOH polymer then being known as partially hydrolyzed, it is more weaklyhydrogen-bonded and less crystalline and is soluble in cold water—lessthan about 50° F. (10° C.). An intermediate cold or hot water solublefilm can include, for example, intermediate partially-hydrolyzed PVOH(e.g., with degrees of hydrolysis of about 94% to about 98%), and isreadily soluble only in warm water—e.g., rapid dissolution attemperatures of about 40° C. and greater. Both fully and partiallyhydrolyzed PVOH types are commonly referred to as PVOH homopolymersalthough the partially hydrolyzed type is technically a vinylalcohol-vinyl acetate copolymer.

The degree of hydrolysis (DH) of the PVOH polymers and PVOH copolymersincluded in the water-soluble films of the present disclosure can be ina range of about 75% to about 99% (e.g., about 79% to about 92%, about86.5% to about 89%, or about 88%, such as for cold-water solublecompositions; about 90% to about 99%, about 92% to about 99%, or about95% to about 99%). As the degree of hydrolysis is reduced, a film madefrom the resin will have reduced mechanical strength but fastersolubility at temperatures below about 20° C. As the degree ofhydrolysis increases, a film made from the polymer will tend to bemechanically stronger and the thermoformability will tend to decrease.The degree of hydrolysis of the PVOH can be chosen such that thewater-solubility of the polymer is temperature dependent, and thus thesolubility of a film made from the polymer, any compatibilizer polymer,and additional ingredients is also influenced. In one option the film iscold water-soluble. A cold water-soluble film, soluble in water at atemperature of less than 10° C., can include PVOH with a degree ofhydrolysis in a range of about 75% to about 90%, or in a range of about80% to about 90%, or in a range of about 85% to about 90%. In anotheroption the film is hot water-soluble. A hot water-soluble film, solublein water at a temperature of at least about 60° C., can include PVOHwith a degree of hydrolysis of at least about 98%.

Other water soluble polymers for use in addition to the PVOH polymersand PVOH copolymers in the blend can include, but are not limited tomodified polyvinyl alcohols, polyacrylates, water-soluble acrylatecopolymers, polyvinyl pyrrolidone, polyethyleneimine, pullulan,water-soluble natural polymers including, but not limited to, guar gum,gum Acacia, xanthan gum, carrageenan, and starch, water-soluble polymerderivatives including, but not limited to, modified starches,ethoxylated starch, and hydroxypropylated starch, copolymers of theforgoing and combinations of any of the foregoing. Yet otherwater-soluble polymers can include polyalkylene oxides, polyacrylamides,polyacrylic acids and salts thereof, celluloses, cellulose ethers,cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylicacids and salts thereof, polyaminoacids, polyamides, gelatines,methylcelluloses, carboxymethylcelluloses and salts thereof, dextrins,ethylcelluloses, hydroxyethyl celluloses, hydroxypropylmethylcelluloses, maltodextrins, and polymethacrylates. Suchwater-soluble polymers, whether PVOH or otherwise are commerciallyavailable from a variety of sources. Any of the foregoing water-solublepolymers are generally suitable for use as film-forming polymers. Ingeneral, the water-soluble film can include copolymers and/or blends ofthe foregoing resins.

The water-soluble polymers (e.g., the PVOH polymer or polymers) can beincluded in the film in an amount in a range of about 30 wt. % or 50 wt.% to about 90 wt. % or 95 wt. %, for example. The weight ratio of theamount of all water-soluble polymers as compared to the combined amountof all plasticizers, compatibilizing agents, and secondary additives canbe in a range of about 0.5 to about 18, about 0.5 to about 15, about 0.5to about 9, about 0.5 to about 5, about 1 to 3, or about 1 to 2, forexample. The specific amounts of plasticizers and other non-polymercomponent can be selected in a particular embodiment based on anintended application of the water-soluble film to adjust filmflexibility and to impart processing benefits in view of desiredmechanical film properties.

Water-soluble polymers for use in the film described herein (including,but not limited to PVOH polymers and PVOH copolymers) can becharacterized by a viscosity in a range of about 3.0 to about 30.0 cP,about 3.0 to about 27.0 cP, about 4.0 to about 24.0 cP, about 4.0 toabout 23.0 cP, about 4.0 cP to about 15.0 cP, or about 6.0 to about 10.0cP, for example at least about 3.0 cP, 4.0 cP, 6.0 cP, 8.0 cP, 10.0 cP,or 12.0 cP and/or up to about 12.0 cP, 16.0 cP, 20.0 cP, 24.0 cP, or30.0 cP. The viscosity of a polymer is determined by measuring a freshlymade solution using a Brookfield LV type viscometer with UL adapter asdescribed in British Standard EN ISO 15023-2:2006 Annex E BrookfieldTest method. It is international practice to state the viscosity of 4%aqueous polyvinyl alcohol solutions at 20° C. Polymeric viscositiesspecified herein in cP should be understood to refer to the viscosity ofa 4% aqueous water-soluble polymer solution at 20° C., unless specifiedotherwise.

It is well known in the art that the viscosity of a water-solublepolymer (PVOH or otherwise) is correlated with the weight-averagemolecular weight (Mw) of the same polymer, and often the viscosity isused as a proxy for Mw. Thus, the weight-average molecular weight of thewater-soluble polymers, including the first PVOH copolymer and thesecond PVOH polymer or second PVOH copolymer, can be in a range of about30,000 to about 175,000, or about 30,000 to about 100,000, or about55,000 to about 80,000, for example.

The water-soluble film can contain other auxiliary agents and processingagents, such as, but not limited to, plasticizers, plasticizercompatibilizers, surfactants, lubricants, release agents, fillers,extenders, cross-linking agents, antiblocking agents, antioxidants,detackifying agents, antifoams, nanoparticles such as layeredsilicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents(e.g., sodium metabisulfite, sodium bisulfite or others), aversiveagents such as bitterants (e.g., denatonium salts such as denatoniumbenzoate, denatonium saccharide, and denatonium chloride; sucroseoctaacetate; quinine; flavonoids such as quercetin and naringen; andquassinoids such as quassin and brucine) and pungents (e.g., capsaicin,piperine, allyl isothiocyanate, and resinferatoxin), and otherfunctional ingredients, in amounts suitable for their intended purposes.Embodiments including plasticizers are preferred. The amount of suchagents can be up to about 50 wt. %, 20 wt %, 15 wt %, 10 wt %, 5 wt. %,4 wt % and/or at least 0.01 wt. %, 0.1 wt %, 1 wt %, or 5 wt %,individually or collectively.

Whether as the first, second, third, or other plasticizer, theplasticizer can include, but is not limited to, glycerin, diglycerin,sorbitol, ethylene glycol, diethylene glycol, triethylene glycol,dipropylene glycol, tetraethylene glycol, propylene glycol, polyethyleneglycols up to 400 MW, neopentyl glycol, trimethylolpropane, polyetherpolyols, sorbitol, 2-methyl-1,3-propanediol, ethanolamines, and amixture thereof. A preferred plasticizer is glycerin, sorbitol,triethyleneglycol, propylene glycol, dipropylene glycol,2-methyl-1,3-propanediol, trimethylolpropane, or a combination thereof.The total amount of the plasticizer can be in a range of about 10 wt. %to about 40 wt. %, or about 15 wt. % to about 35 wt. %, or about 20 wt.% to about 30 wt. %, for example about 20 wt. % to about 25 wt. %, basedon total film weight. Combinations of glycerin, dipropylene glycol, andsorbitol can be used. Optionally, glycerin can be used in an amount ofabout 5 wt % or 10 wt. % to about 30 wt %, or 5 wt % or 10 wt. % toabout 20 wt %, based on total film weight. Optionally, dipropyleneglycol can be used in an amount of about 1 wt. % to about 20 wt. %, orabout 2 wt. % or 3 wt. % to about 10 wt. % or 15 wt. %, based on totalfilm weight. Optionally, sorbitol can be used in an amount of about 1 wt% to about 20 wt %, or about 2 wt % or 3 wt. % to about 10 wt % or 15wt. %, based on total film weight. The specific amounts of plasticizerscan be selected in a particular embodiment based on desired filmflexibility and processability features of the water-soluble film. Atlow plasticizer levels, films may become brittle, difficult to process,or prone to breaking. At elevated plasticizer levels, films may be toosoft, weak, or difficult to process for a desired use.

Suitable surfactants can include the nonionic, cationic, anionic andzwitterionic classes. Suitable surfactants include, but are not limitedto, polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates,alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides(nonionics), polyoxyethylenated amines, quaternary ammonium salts andquaternized polyoxyethylenated amines (cationics), and amine oxides,N-alkylbetaines and sulfobetaines (zwitterionics). Other suitablesurfactants include dioctyl sodium sulfosuccinate, lactylated fatty acidesters of glycerol and propylene glycol, lactylic esters of fatty acids,sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65,polysorbate 80, lecithin, acetylated fatty acid esters of glycerol andpropylene glycol, and acetylated esters of fatty acids, and combinationsthereof. In various embodiments, the amount of surfactant in thewater-soluble film is in a range of about 0.1 wt % to 2.5 wt %,optionally about 1.0 wt % to 2.0 wt %.

Suitable lubricants/release agents can include, but are not limited to,fatty acids and their salts, fatty alcohols, fatty esters, fatty amines,fatty amine acetates and fatty amides. Preferred lubricants/releaseagents are fatty acids, fatty acid salts, and fatty amine acetates. Inone type of embodiment, the amount of lubricant/release agent in thewater-soluble film is in a range of about 0.02 wt % to about 1.5 wt %,optionally about 0.1 wt % to about 1 wt %.

Suitable fillers/extenders/antiblocking agents/detackifying agentsinclude, but are not limited to, starches, modified starches,crosslinked polyvinylpyrrolidone, crosslinked cellulose,microcrystalline cellulose, silica, metallic oxides, calcium carbonate,talc and mica. Preferred materials are starches, modified starches andsilica. In one type of embodiment, the amount offiller/extender/antiblocking agent/detackifying agent in thewater-soluble film is in a range of about 0.1 wt % to about 25 wt %, orabout 1 wt % to about 10 wt %, or about 2 wt. % to about 8 wt. %, orabout 3 wt. % to about 5 wt. %. In the absence of starch, one preferredrange for a suitable filler/extender/antiblocking agent/detackifyingagent is about 0.1 wt % or 1 wt % to about 4 wt % or 6 wt %, or about 1wt. % to about 4 wt. %, or about 1 wt. % to about 2.5 wt. %.

The water-soluble film can further have a residual moisture content ofat least 4 wt. %, for example, or in a range of about 4 to about 10 wt.%, as measured by Karl Fischer titration.

Other features of water-soluble polymer compositions such as films, maybe found in U.S. Publication No. 2011/0189413 and U.S. Publication No.2014/0199460, both of which are incorporated by reference herein intheir entireties.

Method of Making Film

One contemplated class of embodiments is characterized by thewater-soluble film being formed by, for example, admixing, co-casting,or welding the PVOH polymer (or PVOH polymers in the case of a blendsystem) together with the first, second, and third plasticizers alongwith any optional secondary additives described herein. If the polymersare first admixed then the water-soluble film is preferably formed bycasting the resulting admixture (e.g., along with other plasticizers andother additives) to form a film. If the polymers are welded, thewater-soluble film can be formed by, for example, solvent or thermalwelding. Another contemplated class of embodiments is characterized bythe water-soluble film being formed by extrusion, for example, blownextrusion. In one contemplated non-limiting embodiment a PVOH polymerand an acrylamido methylpropanesulfonic acid PVOH terpolymer blendedfilm is formed by blown extrusion.

The film can have any suitable thickness. For example, the film can havea thickness in a range of about 5 to about 200 μm, or in a range ofabout 20 to about 100 μm, or about 40 to about 85 μm, for example 76 μm.

Optionally, the water-soluble film can be a free-standing filmconsisting of one layer or a plurality of like layers. Furtheroptionally, the water-soluble film can have at least one layer and caninclude one or more additional layers of dissimilar composition.

The film is useful for creating an article such as a packet to contain adetergent composition comprising cleaning actives thereby forming apouch. The cleaning actives may take any form such as powders, gels,pastes, liquids, tablets or any combination thereof. The film is alsouseful for any other application in which improved wet handling and lowcold water residues are desired. Embodiments of the film can alsoexhibit favorable mechanical properties (e.g., seal strength, tensilestrength), for example as formed and/or after a period of time undercontrolled aging conditions. The film forms at least one side wall ofthe pouch and/or packet, optionally the entire pouch and/or packet, andpreferably an outer surface of the at least one sidewall.

The film described herein can also be used to make an article such as apacket with two or more compartments made of the same film or incombination with films of other polymeric materials. Additional filmscan, for example, be obtained by casting, blow-molding, extrusion orblown extrusion of the same or a different polymeric material, as knownin the art. In one type of embodiment, the polymers, copolymers orderivatives thereof suitable for use as the additional film are selectedfrom polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides,polyacrylic acid, cellulose, cellulose ethers, cellulose esters,cellulose amides, polyvinyl acetates, polycarboxylic acids and salts,polyaminoacids or peptides, polyamides, polyacrylamide, copolymers ofmaleic/acrylic acids, polysaccharides including starch and gelatin,natural gums such as xanthan, and carrageenans. For example, polymerscan be selected from polyacrylates and water-soluble acrylatecopolymers, methylcellulose, carboxymethylcellulose sodium, dextrin,ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose,maltodextrin, polymethacrylates, and combinations thereof, or selectedfrom polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropylmethyl cellulose (HPMC), and combinations thereof. One contemplatedclass of embodiments is characterized by the level of polymer in thepacket material, for example the PVOH resin blend, as described above,being at least 60%.

Articles

The articles of the present disclosure include water soluble film and acomposition, typically a household care composition, that is proximal tothe film.

The articles of the present disclosure can include pouches that mayinclude at least one sealed compartment. Thus, the pouches may comprisea single compartment or multiple compartments. FIG. 1 illustrates anarticle in which a water-soluble pouch 100 is formed from water-solublepolymer films 10, 20 sealed at an interface 30. One or both of the films10, 20 include the PVOH polymer and first, second, and thirdplasticizers. The films 10, 20 define an interior pouch container volume40 which contains any desired composition 50 for release into an aqueousenvironment. The composition 50 is not particularly limited, for exampleincluding any of the variety of cleaning compositions described below.In embodiments comprising multiple compartments (not shown), eachcompartment may contain identical and/or different compositions. Inturn, the compositions may take any suitable form including, but notlimited to liquid, solid and combinations thereof (e.g. a solidsuspended in a liquid). In some embodiments, the pouches comprises afirst, second and third compartment, each of which respectively containsa different first, second, and third composition.

The compartments of multi-compartment pouches may be of the same ordifferent size(s) and/or volume(s). The compartments of the presentmulti-compartment pouches can be separate or conjoined in any suitablemanner. In some embodiments, the second and/or third and/or subsequentcompartments are superimposed on the first compartment. In oneembodiment, the third compartment may be superimposed on the secondcompartment, which is in turn superimposed on the first compartment in asandwich configuration. Alternatively the second and third compartmentsmay be superimposed on the first compartment. However it is also equallyenvisaged that the first, second and optionally third and subsequentcompartments may be attached to one another in a side by siderelationship. The compartments may be packed in a string, eachcompartment being individually separable by a perforation line. Henceeach compartment may be individually torn-off from the remainder of thestring by the end-user, for example, so as to pre-treat or post-treat afabric with a composition from a compartment. In some embodiments, thefirst compartment may be surrounded by at least the second compartment,for example in a tire-and-rim configuration, or in a pouch-in-a-pouchconfiguration.

In some embodiments, multi-compartment pouches comprise threecompartments consisting of a large first compartment and two smallercompartments. The second and third smaller compartments are superimposedon the first larger compartment. The size and geometry of thecompartments are chosen such that this arrangement is achievable. Thegeometry of the compartments may be the same or different. In someembodiments the second and optionally third compartment each has adifferent geometry and shape as compared to the first compartment. Inthese embodiments, the second and optionally third compartments arearranged in a design on the first compartment. The design may bedecorative, educative, or illustrative, for example to illustrate aconcept or instruction, and/or used to indicate origin of the product.In some embodiments, the first compartment is the largest compartmenthaving two large faces sealed around the perimeter, and the secondcompartment is smaller covering less than about 75%, or less than about50% of the surface area of one face of the first compartment. Inembodiments in which there is a third compartment, the aforementionedstructure may be the same but the second and third compartments coverless than about 60%, or less than about 50%, or less than about 45% ofthe surface area of one face of the first compartment.

The articles, pouches and/or packets of the present disclosure maycomprise one or more different films. For example, in single compartmentembodiments, the packet may be made from one wall that is folded ontoitself and sealed at the edges, or alternatively, two walls that aresealed together at the edges. In multiple compartment embodiments, thepacket may be made from one or more films such that any given packetcompartment may comprise walls made from a single film or multiple filmshaving differing compositions. In one embodiment, a multi-compartmentpouch comprises at least three walls: an outer upper wall; an outerlower wall; and a partitioning wall. The outer upper wall and the outerlower wall are generally opposing and form the exterior of the pouch.The partitioning wall is interior to the pouch and is secured to thegenerally opposing outer walls along a seal line. The partitioning wallseparates the interior of the multi-compartment pouch into at least afirst compartment and a second compartment.

Articles, which may be pouches or packets, may be made using anysuitable equipment and method. For example, single compartment pouchesmay be made using vertical form filling, horizontal form filling, orrotary drum filling techniques commonly known in the art. Such processesmay be either continuous or intermittent. The film may be dampened,and/or heated to increase the malleability thereof. The method may alsoinvolve the use of a vacuum to draw the film into a suitable mold. Thevacuum drawing the film into the mold can be applied for about 0.2 toabout 5 seconds, or about 0.3 to about 3, or about 0.5 to about 1.5seconds, once the film is on the horizontal portion of the surface. Thisvacuum can be such that it provides an under-pressure in a range of 10mbar to 1000 mbar, or in a range of 100 mbar to 600 mbar, for example.

The molds, in which articles such as packets may be made, can have anyshape, length, width and depth, depending on the required dimensions ofthe pouches. The molds may also vary in size and shape from one toanother, if desirable. For example, the volume of the final pouches maybe about 5 ml to about 300 ml, or about 10 to 150 ml, or about 20 toabout 100 ml, and that the mold sizes are adjusted accordingly.

The article (e.g., a packet or a pouch) may comprise a first and asecond sealed compartment. The second compartment is in a generallysuperposed relationship with the first sealed compartment such that thesecond sealed compartment and the first sealed compartment share apartitioning wall interior to the pouch.

The article (e.g., a packet or a pouch) may comprise a first and asecond compartment further comprises a third sealed compartment. Thethird sealed compartment is in a generally superposed relationship withthe first sealed compartment such that the third sealed compartment andthe first sealed compartment share a partitioning wall interior to thepouch.

The first composition and the second composition may be selected fromone of the following combinations: liquid, liquid; liquid, powder;powder, powder; and powder, liquid.

The first, second and third compositions may be selected from one of thefollowing combinations: solid, liquid, liquid and liquid, liquid,liquid.

The single compartment or plurality of sealed compartments may contain acomposition. The plurality of compartments may each contain the same ora different composition. The composition is selected from a liquid,solid or combination thereof.

The composition may be selected from the group of liquid light duty andliquid heavy duty liquid detergent compositions, powdered detergentcompositions, dish detergent for hand washing and/or machine washing;hard surface cleaning compositions, fabric enhancers, detergent gelscommonly used for laundry, and bleach and laundry additives, shampoos,and body washes.

Shaping, Sealing, and Thermoforming

A contemplated class of embodiments is characterized by goodthermoformability of the water-soluble film made as described herein. Athermoformable film is one that can be shaped through the application ofheat and a force.

Thermoforming a film is the process of heating the film, shaping it in amold, and then allowing the film to cool, whereupon the film will holdthe shape of the mold. The heat may be applied using any suitable means.For example, the film may be heated directly by passing it under aheating element or through hot air, prior to feeding it onto a surfaceor once on a surface. Alternatively, it may be heated indirectly, forexample by heating the surface or applying a hot item onto the film. Insome embodiments, the film is heated using an infrared light. The filmmay be heated to a temperature of about 50 to about 150° C., about 50 toabout 120° C., about 60 to about 130° C., about 70 to about 120° C., orabout 60 to about 90° C. Thermoforming can be performed by any one ormore of the following processes: the manual draping of a thermallysoftened film over a mold, or the pressure induced shaping of a softenedfilm to a mold (e.g., vacuum forming), or the automatic high-speedindexing of a freshly extruded sheet having an accurately knowntemperature into a forming and trimming station, or the automaticplacement, plug and/or pneumatic stretching and pressuring forming of afilm.

Alternatively, the film can be wetted by any suitable means, for exampledirectly by spraying a wetting agent (including water, a solution of thefilm composition, a plasticizer for the film composition, or anycombination of the foregoing) onto the film, prior to feeding it ontothe surface or once on the surface, or indirectly by wetting the surfaceor by applying a wet item onto the film.

Once a film has been heated and/or wetted, it may be drawn into anappropriate mold, preferably using a vacuum. The filling of the moldedfilm can be accomplished by utilizing any suitable means. In someembodiments, the most preferred method will depend on the product formand required speed of filling. In some embodiments, the molded film isfilled by in-line filling techniques. The filled, open packets are thenclosed forming the pouches, using a second film, by any suitable method.This may be accomplished while in horizontal position and in continuous,constant motion. The closing may be accomplished by continuously feedinga second film, preferably water-soluble film, over and onto the openpackets and then preferably sealing the first and second film together,typically in the area between the molds and thus between the packets.

Any suitable method of sealing the packet and/or the individualcompartments thereof may be utilized. Non-limiting examples of suchmeans include heat sealing, solvent welding, solvent or wet sealing, andcombinations thereof. Typically, only the area which is to form the sealis treated with heat or solvent. The heat or solvent can be applied byany method, typically on the closing material, and typically only on theareas which are to form the seal. If solvent or wet sealing or weldingis used, it may be preferred that heat is also applied. Preferred wet orsolvent sealing/welding methods include selectively applying solventonto the area between the molds, or on the closing material, by forexample, spraying or printing this onto these areas, and then applyingpressure onto these areas, to form the seal. Sealing rolls and belts asdescribed above (optionally also providing heat) can be used, forexample. One type of embodiment made particularly advantageous by thepresent disclosure is sealing the film to itself of another similar filmby solvent sealing, optionally without heat.

The formed pouches may then be cut by a cutting device. Cutting can beaccomplished using any known method. It may be preferred that thecutting is also done in continuous manner, and preferably with constantspeed and preferably while in horizontal position. The cutting devicecan, for example, be a sharp item, or a hot item, or a laser, whereby inthe latter cases, the hot item or laser ‘burns’ through the film/sealingarea.

The different compartments of a multi-compartment pouches may be madetogether in a side-by-side style wherein the resulting, cojoined pouchesmay or may not be separated by cutting. Alternatively, the compartmentscan be made separately.

In some embodiments, pouches may be made according to a processcomprising the steps of: a) forming a first compartment (as describedabove); b) forming a recess within some or all of the closed compartmentformed in step (a), to generate a second molded compartment superposedabove the first compartment; c) filling and closing the secondcompartments by means of a third film; d) sealing the first, second andthird films; and e) cutting the films to produce a multi-compartmentpouch. The recess formed in step (b) may be achieved by applying avacuum to the compartment prepared in step (a).

In some embodiments, second, and/or third compartment(s) can be made ina separate step and then combined with the first compartment asdescribed in European Patent Application Number 08101442.5 or WO2009/152031.

In some embodiments, pouches may be made according to a processcomprising the steps of: a) forming a first compartment, optionallyusing heat and/or vacuum, using a first film on a first forming machine;b) filling the first compartment with a first composition; c) on asecond forming machine, deforming a second film, optionally using heatand vacuum, to make a second and optionally third molded compartment; d)filling the second and optionally third compartments; e) sealing thesecond and optionally third compartment using a third film; f) placingthe sealed second and optionally third compartments onto the firstcompartment; g) sealing the first, second and optionally thirdcompartments; and h) cutting the films to produce a multi-compartmentpouch.

The first and second forming machines may be selected based on theirsuitability to perform the above process. In some embodiments, the firstforming machine is preferably a horizontal forming machine, and thesecond forming machine is preferably a rotary drum forming machine,preferably located above the first forming machine.

It should be understood that by the use of appropriate feed stations, itmay be possible to manufacture multi-compartment pouches incorporating anumber of different or distinctive compositions and/or different ordistinctive liquid, gel or paste compositions.

The film and/or pouch may be sprayed or dusted with a suitable material,such as an active agent, a lubricant, an aversive agent, or mixturesthereof. The film and/or pouch may be printed upon, for example, with anink and/or an active agent.

Composition

The articles of the present disclosure include a composition, typicallya household care composition. The composition is proximal to thewater-soluble film. The composition may be less than about 10 cm, orless than about 5 cm, or less than about 1 cm from the film. Typicallythe composition is adjacent to the film or in contact with the film. Thefilm may be in the form of a pouch or a compartment, containing thecomposition therein.

The present pouches may contain various compositions. Amulti-compartment pouch may contain the same or different compositionsin each separate compartment.

As described above, the film and pouch are particularly advantageous forpackaging (e.g., in direct contact with) materials which haveexchangeable hydrogen ions, for example compositions characterized byacid/base equilibria, such as amine-fatty acid equilibria and/oramine-anionic surfactant acid equilibria.

This feature of the disclosure may be utilized to keep compositionscontaining incompatible ingredients (e.g., bleach and enzymes)physically separated or partitioned from each other. It is believed thatsuch partitioning may expand the useful life and/or decrease physicalinstability of such ingredients. Additionally or alternatively, suchpartitioning may provide aesthetic benefits as described in EuropeanPatent Application Number 09161692.0.

Non-limiting examples of useful household care compositions includelight duty and heavy duty liquid detergent compositions, hard surfacecleaning compositions, detergent gels commonly used for laundry, bleachand laundry additives, fabric enhancer compositions (such as fabricsofteners), shampoos, body washes, and other personal care compositions.Compositions of use in the present pouches may take the form of aliquid, solid or a powder. Liquid compositions may comprise a solid.Solids may include powder or agglomerates, such as micro-capsules,beads, noodles or one or more pearlized balls or mixtures thereof. Sucha solid element may provide a technical benefit, through the wash or asa pre-treat, delayed or sequential release component; additionally oralternatively, it may provide an aesthetic effect.

The compositions encapsulated by the films described herein can have anysuitable viscosity depending on factors such as formulated ingredientsand purpose of the composition. In one embodiment, the composition has ahigh shear viscosity value, at a shear rate of 20 s⁻¹ and a temperatureof 20° C., of 100 to 3,000 cP, alternatively 300 to 2,000 cP,alternatively 500 to 1,000 cP, and a low shear viscosity value, at ashear rate of 1 s⁻¹ and a temperature of 20° C., of 500 to 100,000 cP,alternatively 1000 to 10,000 cP, alternatively 1,300 to 5,000 cP.Methods to measure viscosity are known in the art. According to thepresent invention viscosity measurements are carried out using arotational rheometer e.g. TA instruments AR550. The instrument includesa 40 mm 2° or 1° cone fixture with a gap of around 50-60 μm forisotropic liquids, or a 40 mm flat steel plate with a gap of 1000 μm forparticles containing liquids. The measurement is carried out using aflow procedure that contains a conditioning step, a peak hold and acontinuous ramp step. The conditioning step involves the setting of themeasurement temperature at 20° C., a pre-shear of 10 seconds at a shearrate of 10 s⁻¹, and an equilibration of 60 seconds at the selectedtemperature. The peak hold involves applying a shear rate of 0.05 s⁻¹ at20° C. for 3 min with sampling every 10 s. The continuous ramp step isperformed at a shear rate from 0.1 to 1200 s⁻¹ for 3 min at 20° C. toobtain the full flow profile.

In articles comprising laundry, laundry additive and/or fabric enhancercompositions, the compositions may comprise one or more of the followingnon-limiting list of ingredients: fabric care benefit agent; detersiveenzyme; deposition aid; rheology modifier; builder; bleach; bleachingagent; bleach precursor; bleach booster; bleach catalyst; perfume and/orperfume microcapsules (see for example U.S. Pat. No. 5,137,646); perfumeloaded zeolite; starch encapsulated accord; polyglycerol esters;whitening agent; pearlescent agent; enzyme stabilizing systems;scavenging agents including fixing agents for anionic dyes, complexingagents for anionic surfactants, and mixtures thereof; opticalbrighteners or fluorescers; polymer including but not limited to soilrelease polymer and/or soil suspension polymer; dispersants; antifoamagents; non-aqueous solvent; fatty acid; suds suppressors, e.g.,silicone suds suppressors (see: U.S. Publication No. 2003/0060390 A1, ¶65-77); cationic starches (see: US 2004/0204337 A1 and US 2007/0219111A1); scum dispersants (see: US 2003/0126282 A1, ¶89-90); substantivedyes; hueing dyes (see: US 2014/0162929A1); colorants; opacifier;antioxidant; hydrotropes such as toluenesulfonates, cumenesulfonates andnaphthalenesulfonates; color speckles; colored beads, spheres orextrudates; clay softening agents; anti-bacterial agents. Any one ormore of these ingredients is further described in described in EuropeanPatent Application Number 09161692.0, U.S. Publication Number2003/0139312A1 and U.S. Patent Application No. 61/229,981. Additionallyor alternatively, the compositions may comprise surfactants, quaternaryammonium compounds, and/or solvent systems. Quaternary ammoniumcompounds may be present in fabric enhancer compositions, such as fabricsofteners, and comprise quaternary ammonium cations that are positivelycharged polyatomic ions of the structure NR₄ ⁺, where R is an alkylgroup or an aryl group.

Surfactants

The detergent compositions can comprise from about 1% to 80% by weightof a surfactant. Surfactant is particularly preferred as a component ofthe first composition. Preferably, the first composition comprises fromabout 5% to 50% by weight of surfactant. The second and thirdcompositions may comprise surfactant at levels of from 0.1 to 99.9%.

Detersive surfactants utilized can be of the anionic, nonionic,zwitterionic, ampholytic or cationic type or can comprise compatiblemixtures of these types. More preferably surfactants are selected fromthe group consisting of anionic, nonionic, cationic surfactants andmixtures thereof. Preferably the compositions are substantially free ofbetaine surfactants. Detergent surfactants useful herein are describedin U.S. Pat. Nos. 3,664,961; 3,919,678; 4,222,905; and 4,239,659.Anionic and nonionic surfactants are preferred.

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,“soaps”, are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodium, potassium, ammonium, andalkyl ammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, and preferably from about 12 to about 18 carbonatoms. Soaps can be made by direct saponification of fats and oils or bythe neutralization of free fatty acids. Particularly useful are thesodium and potassium salts of the mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and coconutsoap.

Additional non-soap anionic surfactants which are suitable for useherein include the water-soluble salts, preferably the alkali metal, andammonium salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl group containing from about 10 to about 20carbon atoms and a sulfonic acid or sulfuric acid ester group. (Includedin the term “alkyl” is the alkyl portion of acyl groups.) Examples ofthis group of synthetic surfactants include: a) the sodium, potassiumand ammonium alkyl sulfates, especially those obtained by sulfating thehigher alcohols (C₈-C₁₈) such as those produced by reducing theglycerides of tallow or coconut oil; b) the sodium, potassium andammonium alkyl polyethoxylate sulfates, particularly those in which thealkyl group contains from 10 to 22, preferably from 12 to 18 carbonatoms, and wherein the polyethoxylate chain contains from 1 to 15,preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassiumalkylbenzene sulfonates in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain or branched chainconfiguration, e.g., those of the type described in U.S. Pat. Nos.2,220,099 and 2,477,383. Especially valuable are linear straight chainalkylbenzene sulfonates in which the average number of carbon atoms inthe alkyl group is from about 11 to 13, abbreviated as C₁₁-C₁₃ LAS.

Preferred nonionic surfactants are those of the formula R₁(OC₂H₄)—OH,wherein R₁ is a C₁₀-C₁₆ alkyl group or a C₅-C₁₂ alkyl phenyl group, andn is from 3 to about 80. Particularly preferred are condensationproducts of C₁₂-C₁₅ alcohols with from about 5 to about 20 moles ofethylene oxide per mole of alcohol, e.g., C₁₂-C₁₃ alcohol condensed withabout 6.5 moles of ethylene oxide per mole of alcohol.

Solvent System

The solvent system in the present compositions can be a solvent systemcontaining water alone or mixtures of organic solvents with water.Preferred organic solvents include 1,2-propanediol, ethanol, glycerol,dipropylene glycol, methyl propane diol and mixtures thereof. Otherlower alcohols, C₁-C₄ alkanolamines such as monoethanolamine andtriethanolamine, can also be used. Solvent systems can be absent, forexample from anhydrous solid embodiments of the disclosure, but moretypically are present at levels in the range of from about 0.1% to about98%, preferably at least about 1% to about 50%, more usually from about5% to about 25%. Typically, the present compositions, particularly whenin liquid form, comprise less than 50% water, preferably from about 0.1%to about 20% water, or more preferably from about 0.5% to about 15%, orfrom about 5% to about 12%, by weight of the composition, of water.

The compositions herein can generally be prepared by mixing theingredients together. If a pearlescent material is used it should beadded in the late stages of mixing. If a rheology modifier is used, itis preferred to first form a pre-mix within which the rheology modifieris dispersed in a portion of the water and optionally other ingredientseventually used to comprise the compositions. This pre-mix is formed insuch a way that it forms a structured liquid. To this structured pre-mixcan then be added, while the pre-mix is under agitation, thesurfactant(s) and essential laundry adjunct materials, along with waterand whatever optional detergent composition adjuncts are to be used.

The pH of the useful compositions may be from about 2 to about 12, about4 to about 12, about 5.5 to about 9.5, about 6 to about 8.5, or about6.5 to about 8.2. Laundry detergent compositions may have a pH of about6 to about 10, about 6.5 to about 8.5, about 7 to about 7.5, or about 8to about 10. Auto-dishwashing compositions may have a pH of about 8 toabout 12. Laundry detergent additive compositions may have a pH of about4 to about 8. Fabric enhancers may have a pH of from about 2 to about 8,or from about 2 to about 4, or from about 2.5 to about 3.5, or fromabout 2.7 to about 3.3.

The pH of the detergent is defined as the pH of an aqueous 10%(weight/volume) solution of the detergent at 20±2° C.; for solids andpowdered detergent this is defined as the pH of an aqueous 1%(weight/volume) solution of the detergent at 20±2° C. Any meter capableof measuring pH to ±0.01 pH units is suitable. Orion meters (ThermoScientific, Clintinpark—Keppekouter, Ninovesteenweg 198, 9320Erembodegem—Aalst, Belgium) or equivalent are acceptable instruments.The pH meter should be equipped with a suitable glass electrode withcalomel or silver/silver chloride reference. An example includes MettlerDB 115. The electrode shall be stored in the manufacturer's recommendedelectrolyte solution.

The 10% aqueous solution of the detergent is prepared according to thefollowing procedure. A sample of 10±0.05 grams is weighted with abalance capable of accurately measuring to ±0.02 grams. The sample istransferred to a 100 mL volumetric flask, diluted to volume withpurified water (deionized and/or distilled water are suitable as long asthe conductivity of the water is <5 μS/cm), and thoroughly mixed. About50 mL of the resulting solution is poured into a beaker, the temperatureis adjusted to 20±2° C. and the pH is measured according to the standardprocedure of the pH meter manufacturer (it is critical to follow themanufacturer's instructions to also set up and calibrate the pHassembly).

For solid and powdered detergents, the 1% aqueous solution of thedetergent is prepared according to the following procedure. A sample of10±0.05 grams is weighted with a balance capable of accurately measuringto ±0.02 grams. The sample is transferred to a volumetric flask of 1000mL, diluted to volume with purified water (deionized and/or distilledwater are suitable as long as the conductivity of the water is <5μS/cm), and thoroughly mixed. About 50 mL of the resulting solution ispoured into a beaker, the temperature is adjusted to 20±2° C. and the pHis measured according to the standard procedure of the pH metermanufacturer (it is critical to follow the manufacturer's instructionsto also set up and calibrate the pH assembly).

Bleaches

Inorganic and organic bleaches are suitable cleaning actives for useherein. Inorganic bleaches include perhydrate salts such as perborate,percarbonate, perphosphate, persulfate and persilicate salts. Theinorganic perhydrate salts are normally the alkali metal salts. Theinorganic perhydrate salt may be included as the crystalline solidwithout additional protection. Alternatively, the salt can be coated asis known in the art.

Alkali metal percarbonates, particularly sodium percarbonate arepreferred perhydrates for use in the detergent composition describedherein. The percarbonate is most preferably incorporated into theproducts in a coated form which provides in-product stability. Asuitable coating material providing in product stability comprises mixedsalt of a water-soluble alkali metal sulphate and carbonate. Suchcoatings together with coating processes have previously been describedin GB1,466,799, and U.S. Pat. Nos. 3,975,280; 4,075,116; and 5,340,496,each incorporated herein by reference. The weight ratio of the mixedsalt coating material to percarbonate lies in the range from 1:99 to1:9, and preferably from 1:49 to 1:19. Preferably, the mixed salt is ofsodium sulphate and sodium carbonate which has the general formulaNa₂SO₄+n+Na₂CO₃ wherein n is from 0.1 to 3, preferably from 0.3 to 1.0,and more preferably from 0.2 to 0.5. Another suitable coating materialproviding in product stability comprises sodium silicate of SiO₂: Na₂Oratio from 1.8:1 to 3.0:1, preferably 1.8:1 to 2.4:1, and/or sodiummetasilicate, preferably applied at a level of from 2% to 10%, (normallyfrom 3% to 5%) of SiO₂ by weight of the inorganic perhydrate salt, suchas potassium peroxymonopersulfate. Other coatings which containmagnesium silicate, silicate and borate salts, silicate and boric acids,waxes, oils, and fatty soaps can also be used advantageously

Organic bleaches can include organic peroxyacids including diacyl andtetraacylperoxides, especially diperoxydodecanedioc acid,diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Dibenzoylperoxide is a preferred organic peroxyacid herein. The diacyl peroxide,especially dibenzoyl peroxide, preferably can be present in the form ofparticles having a weight average diameter of from about 0.1 to about100 microns, preferably from about 0.5 to about 30 microns, morepreferably from about 1 to about 10 microns. Preferably, at least about25% to 100%, more preferably at least about 50%, even more preferably atleast about 75%, most preferably at least about 90%, of the particlesare smaller than 10 microns, preferably smaller than 6 microns.

Other organic bleaches include the peroxy acids, particular examplesbeing the alkylperoxy acids and the arylperoxy acids. Preferredrepresentatives are: (a) peroxybenzoic acid and its ring-substitutedderivatives, such as alkylperoxybenzoic acids, but alsoperoxy-α-naphthoic acid and magnesium monoperphthalate; (b) thealiphatic or substituted aliphatic peroxy acids, such as peroxylauricacid, peroxystearic acid, ε-phthalimidoperoxycaproicacid[phthaloiminoperoxyhexanoic acid (PAP)],o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid andN-nonenylamidopersuccinates; and (c) aliphatic and araliphaticperoxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid,1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid,the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid,N,N-terephthaloyldi(6-aminopercaproic acid)

Bleach activators can include organic peracid precursors that enhancethe bleaching action in the course of cleaning at temperatures of 60° C.and below. Bleach activators suitable for use herein include compoundswhich, under perhydrolysis conditions, give aliphatic peroxoycarboxylicacids having preferably from 1 to 10 carbon atoms, in particular from 2to 4 carbon atoms, and/or optionally substituted perbenzoic acid.Suitable substances bear O-acyl and/or N-acyl groups of the number ofcarbon atoms specified and/or optionally substituted benzoyl groups.Preference is given to polyacylated alkylenediamines, in particulartetraacetylethylenediamine (TAED), acylated triazine derivatives, inparticular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),acylated glycolurils, in particular tetraacetylglycoluril (TAGU),N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylatedphenolsulfonates, in particular n-nonanoyl- orisononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides,in particular phthalic anhydride, acylated polyhydric alcohols, inparticular triacetin, ethylene glycol diacetate and2,5-diacetoxy-2,5-dihydrofuran and also triethylacetyl citrate (TEAC).

Bleach catalysts preferred for use in the detergent composition hereininclude the manganese triazacyclononane and related complexes (U.S. Pat.Nos. 4,246,612, 5,227,084); Co, Cu, Mn and Fe bispyridylamine andrelated complexes (U.S. Pat. No. 5,114,611); and pentamine acetatecobalt(III) and related complexes (U.S. Pat. No. 4,810,410). A completedescription of bleach catalysts suitable for use herein can be found inU.S. Pat. No. 6,599,871, incorporated herein by reference.

Dishwashing Agents

A preferred surfactant for use in automatic dishwashing detergents islow foaming by itself or in combination with other components (e.g. sudssuppressers). Preferred for use herein are low and high cloud pointnonionic surfactants and mixtures thereof including nonionic alkoxylatedsurfactants (especially ethoxylates derived from C₆-C₁₅ primaryalcohols), ethoxylated-propoxylated alcohols (e.g., Olin Corporation'sPOLY-TERGENT® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g.,Olin Corporation's POLY-TERGENT® SLF18B—see WO-A-94/22800), ether-cappedpoly(oxyalkylated) alcohol surfactants, and blockpolyoxyethylene-polyoxypropylene polymeric compounds such as PLURONIC®,REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp.,Wyandotte, Mich.; amphoteric surfactants such as the C₁₂-C₂₀ alkyl amineoxides (preferred amine oxides for use herein include lauryldimethylamine oxide and hexadecyl dimethyl amine oxide), and alkylamphocarboxylic surfactants such as MIRANOL™ C2M; and zwitterionicsurfactants such as the betaines and sultaines; and mixtures thereof.Surfactants suitable for use herein are disclosed, for example, in U.S.Pat. Nos. 3,929,678, 4,259,217, EP-A-0414 549, WO-A-93/08876 andWO-A-93/08874. Surfactants can be present at a level of from about 0.2%to about 30% by weight, more preferably from about 0.5% to about 10% byweight, most preferably from about 1% to about 5% by weight of adetergent composition.

Other Compositions and Additives

Builders suitable for use in the detergent composition described hereininclude water-soluble builders, including citrates, carbonates, silicateand polyphosphates, e.g. sodium tripolyphosphate and sodiumtripolyphosphate hexahydrate, potassium tripolyphosphate and mixedsodium and potassium tripolyphosphate salts.

Enzymes suitable for use in the detergent composition described hereininclude bacterial and fungal cellulases including CAREZYME and CELLUZYME(Novo Nordisk A/S); peroxidases; lipases including AMANO-P (AmanoPharmaceutical Co.), M1 LIPASE and LIPOMAX (Gist-Brocades) and LIPOLASEand LIPOLASE ULTRA (Novo); cutinases; proteases including ESPERASE,ALCALASE, DURAZYM and SAVINASE (Novo) and MAXATASE, MAXACAL, PROPERASEand MAXAPEM (Gist-Brocades); α and β amylases including PURAFECT OX AM(Genencor) and TERMAMYL, BAN, FUNGAMYL, DURAMYL, and NATALASE (Novo);pectinases; and mixtures thereof. Enzymes can be added herein as prills,granulates, or cogranulates at levels typically in the range from about0.0001% to about 2% pure enzyme by weight of the cleaning composition.

Suds suppressers suitable for use in the detergent composition describedherein include nonionic surfactants having a low cloud point. “Cloudpoint” as used herein, is a well known property of nonionic surfactantswhich is the result of the surfactant becoming less soluble withincreasing temperature, the temperature at which the appearance of asecond phase is observable is referred to as the “cloud point.” As usedherein, a “low cloud point” nonionic surfactant is defined as a nonionicsurfactant system ingredient having a cloud point of less than 30° C.,preferably less than about 20° C., and even more preferably less thanabout 10° C., and most preferably less than about 7.5° C. Low cloudpoint nonionic surfactants can include nonionic alkoxylated surfactants,especially ethoxylates derived from primary alcohol, andpolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers. Also, such low cloud point nonionic surfactants caninclude, for example, ethoxylated-propoxylated alcohol (e.g., BASFPOLY-TERGENT SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g.,BASF POLY-TERGENT SLF18B series of nonionics, as described, for example,in U.S. Pat. No. 5,576,281).

Other suitable components for use in the detergent composition describedherein include cleaning polymers having anti-redeposition, soil releaseor other detergency properties. Anti-redeposition polymers for useherein include acrylic acid containing polymers such as SOKALAN PA30,PA20, PAIS, PA10 and SOKALAN CP10 (BASF GmbH), ACUSOL 45N, 480N, 460N(Rohm and Haas), acrylic acid/maleic acid copolymers such as SOKALANCP,5 and acrylic/methacrylic copolymers. Other suitable polymers includeamine-based polymers such as alkoxylated polyalkyleneimines (e.g.,PEI600 E020 and/or ethoxysulfated hexamethylene diamine dimethyl quats),which, optionally, may be quaternized. Soil release polymers for useherein include alkyl and hydroxyalkyl celluloses (U.S. Pat. No.4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof,and nonionic and anionic polymers based on terephthalate esters ofethylene glycol, propylene glycol and mixtures thereof.

Heavy metal sequestrants and crystal growth inhibitors are also suitablefor use in the detergent, for example diethylenetriamine penta(methylenephosphonate), ethylenediamine tetra(methylene phosphonate)hexamethylenediamine tetra(methylene phosphonate), ethylenediphosphonate, hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate,ethylenediaminotetracetate, ethylenediamine-N,N′-disuccinate in theirsalt and free acid forms.

Suitable for use in the detergent composition described herein is also acorrosion inhibitor, for example organic silver coating agents(especially paraffins such as WINOG 70 sold by Wintershall, Salzbergen,Germany), nitrogen-containing corrosion inhibitor compounds (for examplebenzotriazole and benzimadazole—see GB-A-1137741) and Mn(II) compounds,particularly Mn(II) salts of organic ligands.

Other suitable components for use in the detergent composition hereininclude enzyme stabilizers, for example calcium ion, boric acid andpropylene glycol.

Suitable rinse additives are known in the art. Commercial rinse aids fordishwashing typically are mixtures of low-foaming fatty alcoholpolyethylene/polypropylene glycol ethers, solubilizers (for examplecumene sulfonate), organic acids (for example citric acid) and solvents(for example ethanol). The function of such rinse aids is to influencethe interfacial tension of the water in such a way that it is able todrain from the rinsed surfaces in the form of a thin coherent film, sothat no water droplets, streaks, or films are left after the subsequentdrying process. European Patent 0 197 434 B1 describes rinse aids whichcontain mixed ethers as surfactants. Rinse additives such as fabricsofteners and the like are also contemplated and suitable forencapsulation in a film according to the disclosure herein.

Methods of Use

The films and articles described herein, as well as compositionscontained therein, may be used to treat a substrate, e.g., fabric or ahard surface, for example by contacting the substrate with the film,article, and/or composition contained therein. The contacting step mayoccur manually or in an automatic machine, e.g., an automatic (top orfront-loading) laundry machine or an automatic dishwashing machine. Thecontacting step may occur in the presence of water, which may be at atemperature up to about 80° C., or up to about 60° C., or up to about40° C., or up to about 30° C., or up to about 20° C., or up to about 15°C., or up to about 10° C., or up to about 5° C. As noted above, thepresent films and articles made therefrom are particularly suited forcold water dissolution and therefore provide benefits in cold-waterwashes (e.g., from about 1° C. to about 30° C., or from about 5° C. toabout 20° C.). The contacting step may be followed by a multi-rinsecycle or even by a single rinse cycle; because the film has gooddissolution properties, less water is required to dissolve the filmand/or release the contents contained therein.

Specific contemplated aspects of the disclosure are herein described inthe following numbered paragraphs.

1. An article comprising a water-soluble film and a household carecomposition proximal to the film, where the water-soluble filmcomprises: a polyvinyl alcohol (PVOH) polymer; dipropylene glycol as afirst plasticizer; a sugar alcohol as a second plasticizer; and a polyolas a third plasticizer, the third plasticizer being different from thefirst plasticizer and the second plasticizer.

2. An article comprising a water-insoluble film, where water-insolublefilm comprises: a water-insoluble polyvinyl alcohol (PVOH) polymer(e.g., a crosslinked PVOH polymer); dipropylene glycol as a firstplasticizer; a sugar alcohol as a second plasticizer; and a polyol as athird plasticizer, the third plasticizer being different from the firstplasticizer and the second plasticizer.

3. The article of any of the preceding paragraphs, wherein the sugaralcohol is selected from the group consisting of isomalt, maltitol,sorbitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol, andmannitol.

4. The article of the preceding paragraph, wherein the sugar alcohol issorbitol.

5. The article of any of the preceding paragraphs, wherein the polyol isselected from the group consisting of glycerin, diglycerin, ethyleneglycol, diethylene glycol, triethyleneglycol, tetraethylene glycol,polyethylene glycols up to 400 MW, neopentyl glycol, propylene glycol,2-methyl-1,3-propanediol, trimethylolpropane, and polyether polyols.

6. The article of the preceding paragraph, wherein the polyol isglycerin.

7. The article of any of the preceding paragraphs, wherein the sugaralcohol is sorbitol, and the polyol is glycerin.

8. The article of any of the preceding paragraphs, comprising: thepolyvinyl alcohol (PVOH) polymer; dipropylene glycol as the firstplasticizer; sorbitol as the second plasticizer; and glycerin as thethird plasticizer; wherein the first, second, and third plasticizers arepresent in the film in a combined amount in a range of about 5 parts toabout 50 parts total plasticizer per 100 parts total resin (phr) in thefilm.

9. The article of any of the preceding paragraphs, wherein the film issubstantially free from plasticizers other than the than the first,second, and third plasticizers.

10. The article of any of the preceding paragraphs, wherein the filmcomprises a solid plasticizer which has a melting point above about 50°C.

11. The article of the preceding paragraph, wherein the solidplasticizer is also the second plasticizer.

12. The article of any of the preceding paragraphs, wherein the first,second, and third plasticizers are present in the film in a combinedamount in a range of about 5 parts to about 40 parts total plasticizerper 100 parts total resin (phr) in the film.

13. The article of the preceding paragraph, wherein the first, second,and third plasticizers are present in the film in a combined amount in arange of about 10 phr to about 40 phr, or about 20 phr to about 35 phr.

14. The article of any of the preceding paragraphs, wherein: the filmhas an aged tensile strength of at least about 25 MPa as measured by theAged Tensile Strength Test; and the film has a seal tear value of atleast about 170% as measured by the Sum Seal Tear Test.

15. The article of the preceding paragraph, wherein the film has an agedtensile strength of at least about 30 MPa as measured by the AgedTensile Strength Test.

16. The article of the paragraph 14 or 15, wherein: the firstplasticizer is present in the film in an amount in a range of about 10wt. % to about 40 wt. % relative to the combined amount of the first,second, and third plasticizers in the film; the second plasticizer ispresent in the film in an amount in a range of about 10 wt. % to about30 wt. % relative to the combined amount of the first, second, and thirdplasticizers in the film; and the third plasticizer is present in thefilm in an amount in a range of about 40 wt. % to about 70 wt. %relative to the combined amount of the first, second, and thirdplasticizers in the film.

17. The article of any of the preceding paragraphs, wherein: the firstplasticizer is present in the film in an amount in a range of about 10wt. % to about 65 wt. % relative to the combined amount of the first,second, and third plasticizers in the film.

18. The article of any of the preceding paragraphs, wherein: the secondplasticizer is present in the film in an amount in a range of about 10wt. % to about 65 wt. % relative to the combined amount of the first,second, and third plasticizers in the film.

19. The article of any of the preceding paragraphs, wherein: the thirdplasticizer is present in the film in an amount in a range of about 25wt. % to about 80 wt. % relative to the combined amount of the first,second, and third plasticizers in the film.

20. The article of any of the preceding paragraphs, wherein: the firstplasticizer is present in the film in an amount in a range of about 13wt. % to about 46 wt. % relative to the combined amount of the first,second, and third plasticizers in the film; the second plasticizer ispresent in the film in an amount in a range of about 13 wt. % to about58 wt. % relative to the combined amount of the first, second, and thirdplasticizers in the film; and the third plasticizer is present in thefilm in an amount in a range of about 28 wt. % to about 73 wt. %relative to the combined amount of the first, second, and thirdplasticizers in the film.

21. The article of any of the preceding paragraphs, wherein: the firstplasticizer is present in the film in an amount in a range of about 13wt. % to about 38 wt. % relative to the combined amount of the first,second, and third plasticizers in the film; the second plasticizer ispresent in the film in an amount in a range of about 16 wt. % to about58 wt. % relative to the combined amount of the first, second, and thirdplasticizers in the film; and the third plasticizer is present in thefilm in an amount in a range of about 28 wt. % to about 71 wt. %relative to the combined amount of the first, second, and thirdplasticizers in the film.

22. The article of any of the preceding paragraphs, wherein: the firstplasticizer is present in the film in an amount in a range of about 13wt. % to about 58 wt. % relative to the combined amount of the first,second, and third plasticizers in the film; the second plasticizer ispresent in the film in an amount in a range of about 13 wt. % to about58 wt. % relative to the combined amount of the first, second, and thirdplasticizers in the film; and the third plasticizer is present in thefilm in an amount in a range of about 28 wt. % to about 73 wt. %relative to the combined amount of the first, second, and thirdplasticizers in the film.

23. The article of any of the preceding paragraphs, wherein: the firstplasticizer is present in the film in an amount in a range of about 13wt. % to about 50 wt. % relative to the combined amount of the first,second, and third plasticizers in the film; the second plasticizer ispresent in the film in an amount in a range of about 13 wt. % to about50 wt. % relative to the combined amount of the first, second, and thirdplasticizers in the film; and the third plasticizer is present in thefilm in an amount in a range of about 36 wt. % to about 73 wt. %relative to the combined amount of the first, second, and thirdplasticizers in the film.

24. The article of any of the preceding paragraphs, wherein: the firstplasticizer is present in the film in an amount in a range of about 13wt. % to about 45 wt. % relative to the combined amount of the first,second, and third plasticizers in the film; the second plasticizer ispresent in the film in an amount in a range of about 19 wt. % to about52 wt. % relative to the combined amount of the first, second, and thirdplasticizers in the film; and the third plasticizer is present in thefilm in an amount in a range of about 35 wt. % to about 65 wt. %relative to the combined amount of the first, second, and thirdplasticizers in the film.

25. The article of any of the preceding paragraphs, wherein: the firstplasticizer is present in the film in an amount in a range of about 13wt. % to about 39 wt. % relative to the combined amount of the first,second, and third plasticizers in the film; the second plasticizer ispresent in the film in an amount in a range of about 22 wt. % to about38 wt. % relative to the combined amount of the first, second, and thirdplasticizers in the film; and the third plasticizer is present in thefilm in an amount in a range of about 39 wt. % to about 64 wt. %relative to the combined amount of the first, second, and thirdplasticizers in the film.

26. The article of any of the preceding paragraphs, wherein: the firstplasticizer is present in the film in an amount in a range of about 13wt. % to about 19 wt. % relative to the combined amount of the first,second, and third plasticizers in the film; the second plasticizer ispresent in the film in an amount in a range of about 41 wt. % to about52 wt. % relative to the combined amount of the first, second, and thirdplasticizers in the film; and the third plasticizer is present in thefilm in an amount in a range of about 35 wt. % to about 44 wt. %relative to the combined amount of the first, second, and thirdplasticizers in the film.

27. The article of any of the preceding paragraphs, wherein the film hasat least two of the three properties (a), (b), and (c): (a) an agedmelting transition delta elevation of about 12° C. or less as measuredby the Aged Melting Transition Delta Test; (b) an aged adhesion value ofat least about 1300 g/s as measured by the Aged Adhesion Test; and (c)an aged tensile strength of at least about 25 MPa as measured by theAged Tensile Strength Test.

28. The article of any of the preceding paragraphs, wherein the film hasat least two of the three properties (a), (b), and (c): (a) an agedmelting transition delta elevation of about 11° C. or less as measuredby the Aged Melting Transition Delta Test; (b) an aged adhesion value ofat least about 1900 g/s as measured by the Aged Adhesion Test; and (c)an aged tensile strength of at least about 30 MPa as measured by theAged Tensile Strength Test.

29. The article of any of the preceding paragraphs, wherein the film hasat least two of the three properties (a), (b), and (c): (a) an agedmelting transition delta elevation of about 11° C. or less as measuredby the Aged Melting Transition Delta Test; (b) an aged adhesion value ofat least about 2500 g/s as measured by the Aged Adhesion Test; and (c)an aged tensile strength of at least about 32.5 MPa as measured by theAged Tensile Strength Test.

30. The article of any of paragraphs 27 to 29, wherein the film has allthree of the properties (a), (b), and (c).

31. The article of any of the preceding paragraphs, wherein the filmfurther comprises one or more components selected from the groupconsisting of plasticizers other than the first, second, and thirdplasticizers, plasticizer compatibilizers, lubricants, release agents,fillers, extenders, cross-linking agents, antiblocking agents,antioxidants, detackifying agents, antifoams, nanoparticles, bleachingagents, surfactants, and combinations thereof.

32. The article of any of the preceding paragraphs, wherein the PVOHpolymer comprises a PVOH homopolymer consisting essentially of vinylalcohol monomer units and optionally vinyl acetate monomer units.

33. The article of any of the preceding paragraphs, wherein the PVOHpolymer comprises a PVOH copolymer comprising an anionic monomer unit, avinyl alcohol monomer unit, and optionally a vinyl acetate monomer unit.

34. The article of the preceding paragraph, wherein the anionic monomeris selected from the group consisting of vinyl acetic acid, maleic acid,monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethylmaleate, maleic anyhydride, fumaric acid, monoalkyl fumarate, dialkylfumarate, monomethyl fumarate, dimethyl fumarate, fumaric anyhydride,itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconicanhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonicacid, 2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts of the foregoing, esters of the foregoing, andcombinations thereof.

35. The article of paragraph 33, wherein the anionic monomer is selectedfrom the group consisting of acrylamido methylpropanesulfonic acids,alkali metal salts thereof, and combinations thereof.

36. The article of paragraph 33, wherein the anionic monomer is selectedfrom the group consisting of monomethyl maleate, alkali metal saltsthereof, and combinations thereof.

37. The article of any of the preceding paragraphs, wherein the PVOHpolymer comprises a polymer blend comprising two or more different PVOHhomopolymers.

38. The article of any of the preceding paragraphs, wherein the PVOHpolymer comprises a polymer blend comprising two or more different PVOHcopolymers.

39. The article of the preceding paragraph, wherein the polymer blendcomprises a first PVOH copolymer comprising a first anionic monomerunit, and a second PVOH copolymer comprising a second anionic monomerunit different from the first anionic monomer unit.

40. The article of the preceding paragraph, wherein: the first anionicmonomer is selected from the group consisting of acrylamidomethylpropanesulfonic acids, alkali metal salts thereof, andcombinations thereof; and the second anionic monomer is selected fromthe group consisting of monomethyl maleate, alkali metal salts thereof,and combinations thereof.

41. The article of the preceding paragraph, wherein: the first PVOHcopolymer is present in an amount in a range of about 10 wt. % to about80 wt. % of total PVOH polymers in the film; and the second PVOHcopolymer is present in an amount in a range of about 20 wt. % to about90 wt. % of total PVOH polymers in the film.

42. The article of any of the preceding paragraphs, wherein the PVOHpolymer comprises a polymer blend comprising at least one PVOHhomopolymer and at least one PVOH copolymer.

43. The article of any of the preceding paragraphs, wherein the PVOHpolymer has a degree of hydrolysis in a range of about 75% to about 99%.

44. The article of any of the preceding paragraphs, wherein the PVOHpolymer has a 4% solution viscosity at 20° C. in a range of about 4 cPto about 24 cP.

45. The article of any of the preceding paragraphs, wherein the filmfurther comprises a water-soluble polymer which is other than a PVOHpolymer.

46. The article of the preceding paragraph, wherein the water-solublepolymer is selected from the group consisting of polyethyleneimines,polyvinyl pyrrolidones, polyalkylene oxides, polyacrylamides, celluloseethers, cellulose esters, cellulose amides, polyvinyl acetates,polyamides, gelatines, methylcelluloses, carboxymethylcelluloses andsalts thereof, dextrins, ethylcelluloses, hydroxyethyl celluloses,hydroxypropyl methylcelluloses, maltodextrins, starches, modifiedstarches, guar gum, gum Acacia, xanthan gum, carrageenan, polyacrylatesand salts thereof, copolymers thereof, blends thereof, and combinationsthereof.

47. The article of any of the preceding paragraphs, where the articlecomprises: a film of any of the preceding paragraphs comprising a firstsurface of said film solvent-sealed to a second surface of the same filmor to a surface of a second film of any of the preceding paragraphs.

48. An article of any of the preceding paragraphs where the film is inthe form of a pouch defining an interior pouch volume.

49. The article of the preceding paragraph, where the household carecomposition is contained in the interior pouch volume.

50. The article of any of paragraphs 1-49, wherein the article is in theform of a pouch comprising at least one sealed compartment.

51. The article of paragraph 50, wherein the at least one compartmentcomprises at least one wall, wherein the at least one wall comprises thewater-soluble film.

52. The article of any of paragraphs 50-51, wherein the pouch comprisesat least two compartments.

53. The article of any of paragraphs 50-52, wherein a second compartmentis superposed on a first compartment.

54. The article of any of paragraphs 50-53, wherein the pouch comprisesat least three compartments.

55. The article of any of paragraphs 50-54, wherein a second compartmentand a third compartment are superposed on a first compartment.

56. The article of any of paragraphs 50-55, where the household carecomposition is contained in the at least one compartment.

57. The article of any of the preceding paragraphs, wherein thecomposition is selected from the group consisting of light duty liquiddetergents compositions, heavy duty liquid detergent compositions, hardsurface cleaning compositions, detergent gels commonly used for laundry,bleaching compositions, laundry additives, fabric enhancer compositions,shampoos, body washes, other personal care compositions, and mixturesthereof.

58. The article of any of the preceding paragraphs, where the householdcare composition comprises surfactant.

59. The article of any of the preceding paragraphs, wherein thehousehold care composition is in the form of a liquid, solid, a powder,or mixtures thereof.

60. The article of any of the preceding paragraphs, wherein thehousehold care composition is in contact with the water-soluble film.

61. A method of forming an article of any of the paragraphs 1-59, wherethe method includes the steps of: providing the film, where the filmdefines an interior pouch container volume; filling the container volumewith the household care composition; and sealing the film to form asealed compartment, where the sealed compartment contains thecomposition.

62. A method of treating a substrate, where the method includes the stepof contacting the substrate with the article of any of paragraphs 1-60,or compositions contained therein, typically in the presence of water.

63. A method for making a film according to any of the precedingparagraphs, the method comprising: selecting a polyvinyl alcohol (PVOH)polymer, a first plasticizer, a second plasticizer, and a thirdplasticizer; selecting a desired range for at least a first filmproperty and a second film property; forming a plurality of filmscomprising the PVOH polymer, the first plasticizer, the secondplasticizer, and the third plasticizer at different concentrations ofthe PVOH polymer, the first plasticizer, the second plasticizer, and thethird plasticizer, wherein at least one of the films has a film propertywithin the desired range for each of the first and second filmproperties; determining the first and second film properties for each ofthe formed films; identifying a film concentration for each of the PVOHpolymer, the first plasticizer, the second plasticizer, and the thirdplasticizer from the formed plurality of films, the identified filmconcentration having a first film property and a second film propertywithin the desired range for each property; and forming a filmcomprising the PVOH polymer, the first plasticizer, the secondplasticizer, and the third plasticizer at the identified filmconcentration.

64 Use of dipropylene glycol as a plasticizer for a water-solublepolyvinyl alcohol film, in combination with a sugar alcohol plasticizerand a polyol plasticizer, for improving one or more of (a) aged meltingtransition delta elevation of the film as measured by the Aged MeltingTransition Delta Test; (b) aged adhesion value of the film as measuredby the Aged Adhesion Test; and (c) aged tensile strength of the film asmeasured by the Aged Tensile Strength Test.

Aged Tensile Strength Test

A water-soluble film characterized by or to be tested for tensilestrength according to the Aged Tensile Strength (“ATS” or“Tensile-Aged”) Test and optionally modulus (or tensile stress) isanalyzed as follows. The procedure includes the determination of tensilestrength and optionally the determination of modulus at 100% elongationaccording to ASTM D 882 (“Standard Test Method for Tensile Properties ofThin Plastic Sheeting”) or equivalent. An INSTRON tensile testingapparatus (Model 5544 Tensile Tester or equivalent) is used for thecollection of film data. A film sample of size capable to produceminimum of three test specimens is first conditioned by placing the filmsample in a foil laminate pouch with minimal head space and heat sealedclosed. The pouch is placed in 35° C. oven for 14 days. After the 14days, the pouch is removed and allowed to cool to 23° C. The specimensare each cut with reliable cutting tools to ensure dimensional stabilityand reproducibility, and they are tested in the machine direction (MD)(where applicable) for each measurement. Tests are conducted in thestandard laboratory atmosphere of 23±2.0° C. and 35±5% relativehumidity. For tensile strength or modulus determination, 1″-wide (2.54cm) samples of a single film sheet having a thickness of 3.0±0.15 mil(or 76.2±3.8 μm) are prepared. The sample is then transferred to theINSTRON tensile testing machine to proceed with testing while minimizingexposure in the 35% relative humidity environment. The tensile testingmachine is prepared according to manufacturer instructions, equippedwith a 500 N load cell, and calibrated. The correct grips and faces arefitted (INSTRON grips having model number 2702-032 faces, which arerubber coated and 25 mm wide, or equivalent). The samples are mountedinto the tensile testing machine and analyzed to determine the tensilestrength (i.e., stress required to break film) and optionally the 100%modulus (i.e., stress required to achieve 100% film elongation).

Suitable behavior of water-soluble films according to the disclosure ismarked by ATS values of at least about 25 MPa, 30 MPa, or 32.5 MPa asmeasured by the ATS Test. Generally, higher ATS values are desirablebecause they correspond to stronger pouches in general and strongerpouch seals when the film is the limiting or weakest element of a seal.In various embodiments, the water-soluble film has an ATS value of atleast about 25, 30, 32.5, or 35 MPa and/or up to about 30, 35, 38, 40,45, or 50 MPa.

Sum Seal Tear Test

A water-soluble film characterized by or to be tested for seal strengthaccording to the Sum Seal Tear (“SST” or “Sum % Seal Tears”) Test isanalyzed as follows. The procedure includes the determination of sealstrength as a percent (or fraction) of seals in which the film tearsinstead of the layers of film forming the seal peeling when pulledapart. A strong seal exhibits a tear result (i.e., enough force isapplied to tear the film before a seal is peeled apart), while a weakseal exhibits a peel result (i.e., two sealed films peel apart beforeenough force is applied to tear the film). An INSTRON tensile testingapparatus (Model 5544 Tensile Tester or equivalent) is used for thecollection of film data and an ESIPROOF proofing apparatus or equivalentwith an anilox roller 140/10 is used for sealing two sheets of film withwater. A film sample of size capable to produce a minimum of five testspecimens is first conditioned by placing the film specimens in a foillaminate pouch with minimal head space and heat sealed closed. The pouchis placed in 38° C. oven for 11 days. After the 11 days, the pouch isremoved and allowed to cool to 23° C.±2.0° C.

The SST Test is performed as follows: Prepare the test specimens bycutting four 100 mm×300 mm film sheets with the 300 mm dimension in themachine direction (MD). For two sheets, tape the four corners of onesheet to a surface. Overlay the other sheet on top of the taped sheet sothe appropriate surfaces are in contact. On top of the other tapedsheet, place the remaining sheet on top so that either (1) the glossside (i.e., the substrate-contacting side of a cast film) is contactedwith the matte surface side (i.e., the air-dried side of a cast film),i.e., to form and evaluate a matte-gloss seal or (2) the matte side iscontacted with the matte surface (i.e., to form and evaluate amatte-matte seal). Tape one 100 mm end of the each top sheet to secureto the bottom sheet. Thread the loose end of each top sheet through theESIPROOF proofing roller using the 140/10 anilox roller. Apply 0.5 mL ofwater to the doctor blade. Pull the roller at a constant speed (75 mmper second) to coat the upper film and secure to the lower sheet. Allowthe film to weld for 10-15 minutes. Using a strip punch or samplecutter, cut 25.4 mm wide samples in the transverse direction (TD). Oncetransferred to the INSTRON testing machine proceed with testing tominimize exposure to environment. Set a 6 mm separation between the filmgrips and the cross head speed at 254 mm/min Place the unsealed flaps ofa specimen in the grips of the testing machine, taking care to ensurethe specimen is aligned with the grips and parallel to them. Initiatethe test to apply a load to the flaps to tear or separate the sealedlayers. Record seal performance as a tear if at least one of the twoflaps exhibits a tear in at least 25% of the flap's width. Otherwise,record seal performance as a peel.

The test is performed for both matte-gloss seal specimens andmatte-matte seal specimens, both of which seal configurations are commonin the formation of seals for water-soluble pouches according to thedisclosure. The percent of seals which tear for each type of seal areadded together to provide the SST value. For example, if 100% of thematte-gloss seals tear and 100% of the matte-matte seals tear, the SSTvalue is 200%.

Suitable behavior of water-soluble films according to the disclosure ismarked by SST values of at least about 50%, 100%, 150%, 170%, 180% or190% and/or up to about 160%, 180% or 200% (e.g., about 170% or 180% to200%). Within these ranges, the films exhibit a high seal strength.

Aged Melting Transition Delta Test

A water-soluble film characterized by or to be tested for an increase inmelting temperature according to the Aged Melting Transition Delta Test(“AMTD” or “dTm1”) Test is analyzed as follows. The AMTD value is themelting temperature T_(m1) value after two weeks of aging/annealingminus the T_(m1) value at prior to aging. The melting point of a polymercan increase as the crystallite size/number in the polymer increases.Lower values of AMTD have been associated with better sealing in theconversion process and are believed to be indicative of less growth incrystallinity and thereby providing more mobile, amorphous regionsavailable for sealing. A lower AMTD value is favorable. For aging, afilm sample is first conditioned by being placed in a foil laminatepouch with minimal head space and heat sealed closed. The pouch isplaced in 35° C. oven for 14 days. After the 14 days, the pouch isremoved and allowed to cool to room temperature (23.0° C.±2.0° C.).

The test is performed using a TA Instruments Q2000 differential scanningcalorimeter (DSC) or equivalent with a 50 ml/min nitrogen purge andTZERO aluminum hermetic pans (available from TA Instruments) to avoidweight losses during temperature ramping. Film specimens to be testedare cut in small pieces to provide about 3-5 mg total sample that fitsinto the pans (e.g., about 3 stacked, cut film pieces). The DSC test isperformed by (1) equilibrating at −75.00° C. and then (2) ramping at10.00° C./min to 200.00° C. to generate DSC curves. Upon generating thecurves, all transitions are recorded as T_(g), T_(m1), and T_(m2), aswell as the enthalpy for T_(m1) according to standard calorimetryanalysis. The DSC test is performed on the initial film prior to agingand the film after two weeks of aging at 35° C. The AMTD value is thencomputed as T_(m1, aged)−T_(m1, initial).

Suitable behavior of water-soluble films according to the disclosure ismarked by AMTD values of about 4, 6, 8, 10, 11, or 12° C. or less and/orat least about 0, 2, 4, 6, or 8° C. (e.g., about 0, 2, or 4° C. to about11 or 12° C.). Within these ranges, the films exhibit improved sealstrength, in particular after formation into packets or pouches.

Aged Adhesion Test

A water-soluble film characterized by or to be tested for adhesion (ortackiness) according to the Aged Adhesion (“AA” or “2W-PA”) Test isanalyzed as follows. The AA test value is the positive area under thecurve of a tackiness (adhesion) test. The positive area is similar to orequivalent to work of adhesion. For aging, a film sample capable toproduce a minimum of three test specimens is first conditioned by beingplaced in a foil laminate pouch with minimal head space and heat sealedclosed. The pouch is placed in 35° C. oven for 14 days. After the 14days, the pouch is removed and allowed to cool to room temperature(23.0° C.±2.0° C.). A higher AA value is favorable and is representativeof seal strength.

The test is performed using a Stable Microsystems (XT+ specification)texture analyzer or equivalent fitted with a pasta firmness rig and anoverhead probe spray gun (BADGER 200-3 or equivalent) for waterapplication. The test is performed with the following standard tackinessmethod parameters: Coat Weight 0.04 g, Open Time 10 sec, Sealing Force50 kg, Sealing Time 2 sec, and Curing Time 60 sec. Samples are preparedunder controlled conditions (21° C., 35% RH) by cutting two film piecesof 14 cm×9 cm and then, using double-sided tape, fixing one layer to thepasta firmness rig (lower platform) and one layer to the upper probe bycarefully smoothing out any potential wrinkle. Three specimen replicatesare then tested according to the following procedure:

1. Position the spray gun at 20.5 cm above the lower platform;

2. Spray water in order to apply 0.04 g at the center of the lower filmlayer;

3. Bring upper probe down until combining film layers and apply 50 kgpressure for 2 s, with the time between water application and combiningbeing set at 10 s;

4. Release pressure and maintain contact for 60 s (force for relaxationat 100 g);

5. Bring upper probe back-up at a constant speed of 12 mm/s; and

6. Record ‘positive area’ as the work of adhesion of the film specimen.

Suitable behavior of water-soluble films according to the disclosure ismarked by AA values of at least about 1300, 1900, or 2500 g/s and/or upto about 3000, 4500, 6000, 8000, 10000, 15000 or 20000 g/s. Above theselower threshold levels (e.g., within a range also defined by an upperbound), the films exhibit improved seal strength.

EXAMPLES Example 1: Plasticizer Blend Series 1

Example 1 represents a series of water-soluble films based on a blend ofPVOH homopolymers and three different plasticizers, including glycerin,sorbitol, and one from a series of different polyol plasticizers. ThePVOH homopolymer blend is a 50 wt. %/50 wt. % blend of a first partiallyhydrolyzed PVOH homopolymer having a 13 cP 4% solution viscosity and asecond partially hydrolyzed PVOH homopolymer having a 23 cP 4% solutionviscosity. The films included (i) their respective PVOH homopolymerresins (100 weight parts per hundred resin weight parts (phr)), (ii)glycerin plasticizer (21.7 phr), (iii) sorbitol plasticizer (5.7 phr),(iv) a polyol plasticizer (11 phr), (v) a modified starch filler (about2-4 phr), (vi) surfactants and other process aids (about 5-7 phr), and(vii) residual water. The polyol plasticizer was variously propyleneglycol (PG), 2-methyl-1,3-propanediol (2M-1,3-PD), diethylene glycol(DEG), trimethylolpropane (TMP), dipropylene glycol (DPG), triethyleneglycol (TEG), or diglycerin (DG). Total plasticizer loading was 38.4phr. Aqueous compositions of the foregoing were cast to form 3.0±0.15mil (or 76.2±3.8 μm) film samples, which were tested for their ATSvalues and SST values by the above methods. Table 1 summarizes the filmproperties, including the molar volume (MVol; ml/mol) of the polyolplasticizer, for Example 1.

TABLE 1 Film Data for Example 1 MVol ATS SST Film Polyol (ml/mol) HSP(MPa) (%) 1 PG 73.7 20.8 31.31 160 2 2M-1,3-PD 88.5 20.5 27.38 140 3 DEG95.3 21.4 29.58 60 4 TMP 121.1 20.8 24.92 140 5 DPG 131.8 20.5 30.33 2006 TEG 134.2 21.2 23.13 160 7 DG 126.0 22.3 22.20 0

FIG. 2 of Example 1 shows that there is a generally unfavorable trend ofdecreasing Aged Tensile-Strength as a function of increasing molarvolume. The general inverse relationship between molar volume and thetensile strength observed is consistent with the role of molar volume inaffecting plasticizer function. The molar volume of a particularplasticizer (e.g., which can be determined as the inverse of plasticizerdensity at 25° C., expressed on a molar basis) generally relates to thesize of plasticizer molecules. Larger plasticizer molecules with largermolar volumes tend to have a more tortuous path adjacent polymer chainsegments (e.g., from the same or different polymer chains), which canlimit the ability of the molecule to function as a plasticizer. FIG. 2shows a reasonable R² correlation value of 88% when DPG is eliminatedfrom the data trend. FIG. 2 illustrates that DPG clearly stands alonefrom among other polyol plasticizers in the blend, because it has asurprisingly high Aged Tensile-Strength notwithstanding its relativelyhigh molar volume and the substantially lower Aged Tensile-Strengths ofother polyol plasticizers having comparable molar volumes (TMP, DG,TEG). Similar to plasticizer molar volume, the Hansen SolubilityParameter (“HSP” or “&r”) has been used to select plasticizers. As seenin Table 2, however, there is no identifiable correlation between theHSP value and the Aged Tensile Strength.

FIG. 3 of Example 1 further shows that DPG has a surprisingly high SumSeal Tear value. The SST value is the sum of percentage water seals thatfail in the tear mode in matte-matte seals and matte-gloss seals, whichrepresent common seal configurations for water-soluble film packets. Thehighest possible SST value is 200%, and this was achieved with only DPGas the third plasticizer in the combination of glycerin, polyol andsorbitol.

Example 2: Plasticizer Blend Series 2

Example 2 represents a series of water-soluble films based on a blend ofPVOH homopolymers and three different plasticizers, including glycerin,one from a series of sugar alcohol plasticizers, and propylene glycol(PG) or dipropylene glycol (DPG). The PVOH homopolymer blend is a 50 wt.%/50 wt. % blend of a first partially hydrolyzed PVOH homopolymer havinga 13 cP 4% solution viscosity and a second partially hydrolyzed PVOHhomopolymer having a 23 cP 4% solution viscosity. The films included (i)their respective PVOH homopolymer resins (100 weight parts per hundredresin weight parts (phr)), (ii) glycerin plasticizer (21.7 phr), (iii) asugar alcohol plasticizer (5.7 phr), (iv) propylene glycol ordipropylene glycol plasticizer (11 phr), (v) a modified starch filler(about 2-4 phr), (vi) surfactants and other process aids (about 5-7phr), and (vii) residual water. The sugar alcohol was variously sorbitol(S), xylitol (X), or mannitol (M). Total plasticizer loading was 38 phr.Aqueous compositions of the foregoing were cast to form 3.0±0.15 mil (or76.2±3.8 μm) film samples, which were tested for their SST values by theabove method. Table 2 summarizes the film properties for Example 2, andit shows that films including a combination of sorbitol and dipropyleneglycol achieve the maximum possible SST value of 200%.

TABLE 2 Film Data for Example 2 SST Film Sugar Alcohol Polyol (%) 1 S PG160 2 X PG 20 3 M PG 0 4 S DPG 200

Example 3: Plasticizer Blend Series 3

Example 3 represents a series of water-soluble films based on a blend ofPVOH copolymers and three different plasticizers, including glycerin,one from a series of sugar alcohol plasticizers, and dipropylene glycol.The PVOH copolymer blend is a 80 wt. %/20 wt. % blend of a firstpartially hydrolyzed PVOH copolymer including monomethyl maleate (sodiumsalt) comonomer (MMM) and a second partially hydrolyzed PVOH copolymerincluding an acrylamido methylpropanesulfonic acid (sodium salt)comonomer (AMPS). The films included (i) their respective PVOH copolymerresins (100 weight parts per hundred resin weight parts (phr)), (ii)glycerin plasticizer (16.2 phr), (iii) a sugar alcohol plasticizer (10.4phr), (iv) dipropylene glycol plasticizer (10.4 phr), (v) a modifiedstarch filler (about 2-4 phr), (vi) surfactants and other process aids(about 5-7 phr), and (vii) residual water. The sugar alcohol wasvariously sorbitol (S), xylitol (X), or mannitol (M). Total plasticizerloading was 37 phr. Aqueous compositions of the foregoing were cast toform 3.0±0.15 mil (or 76.2±3.8 μm) film samples, which were tested fortheir SST values by the above method. Table 3 summarizes the filmproperties for Example 3, and it shows that films including acombination of sorbitol and dipropylene glycol achieve substantiallyimproved SST values compared to other sugar alcohol plasticizers (e.g.,60% for sorbitol, 0% for xylitol and mannitol).

TABLE 3 Film Data for Example 3 SST Film Sugar Alcohol (%) 1 S 60 2 X 03 M 0

Example 4: Plasticizer Blend Series 4

Example 4 represents a series of water-soluble films based on a blend ofPVOH copolymers and three different plasticizers, including glycerin,sorbitol, and dipropylene glycol. The PVOH copolymer blend is a 80 wt.%/20 wt. % blend of a first partially hydrolyzed PVOH copolymerincluding monomethyl maleate (sodium salt) comonomer (MMM) and a secondpartially hydrolyzed PVOH copolymer including an acrylamidomethylpropanesulfonic acid (sodium salt) comonomer (AMPS). The filmsincluded (i) their respective PVOH copolymer resins (100 weight partsper hundred resin weight parts (phr)), (ii) glycerin plasticizer (G;variable phr), (iii) sorbitol plasticizer (S; variable phr), (iv)dipropylene glycol plasticizer (DPG; variable phr), (v) a modifiedstarch filler (about 2-4 phr), (vi) surfactants and other process aids(about 5-7 phr), and (vii) residual water. Total plasticizer loading was29.6 phr, 37.0 phr, or 44.4 phr, and the relative ratios between thethree plasticizers were varied in the films. Aqueous compositions of theforegoing were cast to form 3.0±0.15 mil (or 76.2±3.8 μm) film samples,which were tested for their ATS values, AA values, AMTD values, SSTvalues by the above methods. Table 4 summarizes the film properties forExample 4, and it shows that films including a combination of sorbitoland dipropylene glycol achieve a combination of favorable propertiesover a range of plasticizer blend relative compositions and totalloadings. For example, films according to the disclosure can beformulated to have at least two of the properties: (a) an AMTD value ofabout 12° C. or 11° C. less, (b) an AA value of at least about 1300 g/s,1900 g/s, or 2500 g/s, and (c) an ATS value of at least about 25 MPa, 30MPa, or 32.5 MPa.

TABLE 4 Film Data for Example 4 Total Plast. SST AMTD Film G (phr) S(phr) DPG (phr) (phr) ATS (MPa) (%) (° C.) AA (g/s) 1 8.6 17.0 4.0 29.632.0 0 9.93 2896 2 21.6 4.0 4.0 29.6 28.9 60 7.63 2483 3 8.6 4.0 17.029.6 32.1 80 12.28 1981 4 12.9 8.3 8.3 29.6 32.3 20 9.37 2149 5 10.821.3 5.0 37.0 36.4 0 13.32 1276 6 27.0 5.0 5.0 37.0 26.1 0 4.99 1193 710.8 5.0 21.3 37.0 30.7 20 10.63 788 8 16.2 10.4 10.4 37.0 25.5 60 11.921406 9 12.9 25.5 6.0 44.4 27.4 0 6.35 909 10 32.4 6.0 6.0 44.4 22.9 09.59 644 11 12.9 6.0 25.5 44.4 26.3 20 −1.2 211 12 19.4 12.5 12.5 44.425.3 0 9.89 874

Example 4 illustrates a series of films in which the ratios of the threeplasticizers (G, S, DPG) were varied and evaluated at three totalplasticizer loadings (29.6, 37.0, and 44.4 phr). As generally seen inTable 4, the ATS value, the AMTD value, and the AA value generallyimprove with lower total plasticizer (e.g., 29.6 phr is better than 37.0phr which is better than 44.4 phr in Example 4), in particular forcombinations of properties and with respect to threshold propertiesrepresenting desirable end-use characteristics for the properties. Basedon the results of Example 4, first, second, and third target thresholdlevels for the ATS, AMTD, and AA values were identified: (1) at least 25MPa, 12° C. or less, and at least 1300 g/s; (2) at least 30 MPa, 11° C.or less, and at least 1900 g/s; and (3) at least 32.5 MPa, 11° C. orless, and at least 2500 g/s. FIG. 4 for Example 4 shows contour plots ofAMTD (dTm1), AA (2W-PA), and ATS (Tensile-Aged) values. Each plot has anarrow that shows the direction of favorable performance that isdecreasing AMTD, increasing AA and increasing ATS. There are twoparticularly notable points in this series of plots. Firstly, using AMTDas an example, it is apparent that at 44.4 phr the arrow is pointed downwhile at 37.0 phr the arrow is descending from left to right, andfinally at 29.6 phr the arrow is pointing up. The simplex plots and thecorresponding Table 4 do not identify a formulation that simultaneouslyoptimizes all of individual performance criteria (e.g., maximizing AAand ATS values while minimizing the AMTD value). However there is aformulation space wherein two or three of the performance criteria meetor exceed desirable threshold values.

FIGS. 5-8 illustrate overlaid contour plots with each of three targetthreshold levels for the ATS, AMTD, and AA values described above. Thewhite space in a plot shows the region where all three criteria are metat that level of total plasticizer and ratio of plasticizers, while thegray space show the region where at least one criterion is not met. Forexample, in FIG. 5, the line labeled “A” indicates the boundary betweenfilm compositions having an AMTD value greater than 12° C. (gray region)and those having an AMTD value lower than 12° C. (white region). At thelowest level plasticizer loading level (29.6 phr), decreasing regions ofwhite area from left to right correspond to the first, second, and thirdtarget threshold levels, respectively.

Example 5: PVOH Copolymer Blend Series

Example 5 represents a series of water-soluble films based on a blend ofPVOH copolymers and three different plasticizers, including glycerin,sorbitol, and dipropylene glycol. The PVOH copolymer blend is avariable-ratio blend of a first partially hydrolyzed PVOH copolymerincluding monomethyl maleate (sodium salt) comonomer (MMM) and a secondpartially hydrolyzed PVOH copolymer including an acrylamidomethylpropanesulfonic acid (sodium salt) comonomer (AMPS). The filmsincluded (i) their respective PVOH copolymer resins (100 weight partsper hundred resin weight parts (phr)), (ii) glycerin plasticizer (16.2phr), (iii) sorbitol plasticizer (10.4 phr), (iv) dipropylene glycolplasticizer (10.4 phr), (v) a modified starch filler (about 2-4 phr),(vi) surfactants and other process aids (about 5-7 phr), and (vii)residual water. Total plasticizer loading was 37 phr. The amount ofPVOH-co-MMM in the copolymer blend ranged from 0 wt. % to 100 wt. %.Aqueous compositions of the foregoing were cast to form 3.0±0.15 mil (or76.2±3.8 μm) film samples, which were tested for their ATS values, AAvalues, AMTD values, SST values by the above methods. Table 5 summarizesthe film properties for Example 5, and it shows that films including acombination of sorbitol and dipropylene glycol achieve a combination offavorable properties over a range of copolymer blend compositions.

TABLE 5 Film Data for Example 5 PVOH- co-MMM PVOH-co-AMPS ATS SST AMTDAA Film (wt. %) (wt. %) (MPa) (%) (° C.) (g/s) 1 0 100 17.5 0 10.3 10552 80 20 25.5 60 11.92 1406 3 50 50 25.4 0 7.84 759 4 20 80 22.1 0 9.12611 5 100 0 26.8 20 16.4 1677

FIG. 9 of Example 5 shows that the response of both the AMTD values andthe ATS values is non-linear as function of PVOH-co-MMM (% M) content.This non-linear response is a substantially favorable deviation relativeto a linearly interpolated baseline from the Rule-of Mixtures (ROM).There is a substantial decrease in the AMTD value over a range of about20 wt. % to 80 wt. % PVOH-co-MMM and there is a substantial increase inthe ATS value over a range of about 20 wt. % to 50 wt. % PVOH-co-MMM.FIG. 10 of Example 5 shows that the 80 wt. %/20 wt. % blend ofPVOH-co-MMM/PVOH-co-AMPS shows a surprisingly good SST value compared toall other ratios tested. Although the SST value of 60% is lower comparedto the 200% SST value from Example 1, the 80 wt. %/20 wt. % blend standsout for relatively good performance in the series of Example 5.

Example 6: Illustrative Compositions

Tables 6-14 show illustrative compositions that may comprise thearticles described herein. For example, the compositions below, whichare intended to be non-limiting examples, may be encapsulated in thewater-soluble films described herein, for example in a pouch.

A bleach additive can include the ingredients presented in Table 6.

TABLE 6 A Wt. % Sodium Percarbonate 25 Bleach activator¹ 7 SodiumCarbonate 15 Sodium Citrate 10 Zeolite 10 Sodium Sulfate 15 Enzymes 2Optical brighteners 2 Miscellaneous To 100 ¹Tetraacetyl ethylene diamine

Granular laundry detergents can include the ingredients presented inTable 7.

TABLE 7 B C D E F G (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) Linearalkylbenzenesulfonate 8 7.1 7 6.5 7.5 7.5 AE3S 0 4.8 0 5.2 4 4 C12-14Allylsulfate 1 0 1 0 0 0 AE7 2.2 0 3.2 0 0 0 C₁₀₋₁₂ Dimethylhydroxyethylammonium 0.75 0.94 0.98 0.98 0 0 chloride Crystallinelayered silicate (δ-Na₂Si₂O₅) 4.1 0 4.8 0 0 0 Zeolite A 5 0 5 0 2 2Citric Acid 3 5 3 4 2.5 3 Sodium Carbonate 15 20 14 20 23 23 Silicate 2R(SiO₂:Na₂O at ratio 2:1) 0.08 0 0.11 0 0 0 Soil release agent 0.75 0.720.71 0.72 0 0 Acrylic Acid/Maleic Acid Copolymer 1.1 3.7 1.0 3.7 2.6 3.8Carboxymethylcellulose 0.15 1.4 0.2 1.4 1 0.5 Protease - Purafect ® (84mg active/g) 0.2 0.2 0.3 0.15 0.12 0.13 Amylase - Stainzyme Plus ® (20mg 0.2 0.15 0.2 0.3 0.15 0.15 active/g) Lipase - Lipex ® (18.00 mgactive/g) 0.05 0.15 0.1 0 0 0 Amylase - Natalase ® (8.65 mg active/g)0.1 0.2 0 0 0.15 0.15 Cellulase - Celluclean ™ (15.6 mg 0 0 0 0 0.1 0.1active/g) TAED 3.6 4.0 3.6 4.0 2.2 1.4 Percarbonate 13 13.2 13 13.2 1614 Na salt of Ethylenediamine-N,N′- 0.2 0.2 0.2 0.2 0.2 0.2 disuccinicacid, (S,S) isomer (EDDS) Hydroxyethane di phosphonate (HEDP) 0.2 0.20.2 0.2 0.2 0.2 MgSO₄ 0.42 0.42 0.42 0.42 0.4 0.4 Perfume 0.5 0.6 0.50.6 0.6 0.6 Suds suppressor agglomerate 0.05 0.1 0.05 0.1 0.06 0.05 Soap0.45 0.45 0.45 0.45 0 0 Sulphonated zinc phthalocyanine (active) 0.00070.0012 0.0007 0 0 0 S-ACMC 0.01 0.01 0 0.01 0 0 Direct Violet 9 (active)0 0 0.0001 0.0001 0 0 Sulfate/Water & Miscellaneous Balance to 100

Liquid laundry detergents can include the ingredients presented in Table8.

TABLE 8 H I J K L M Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Glycerol 3 5 6.10.6 5 5.3 1,2 Propanediol 16 14 15.9 12 10 Citric acid 1 1.2 0.5 0.5Isopropanol 7.7 NaOH 0.5 1 Marlipal C₁₂₋₁₄EO₇ 22 11.8 14 20.1 C₁₃₋₁₅EO₉1 15 C₉₋₁₁EO₉ 72 Linear alkyl benzene 16 25 14.5 23 24.6 sulfonic acid¹C₁₂₋₁₈ Fatty acid 16 5 12.5 6 16.4 C₁₂₋₁₄ alkyl 11.1 9 ethoxy 3 sulfateEnzymes 2.5 1.5 1.3 2.0 1.5 2.0 Polyethyleneimine 2 5.0 3.0 ethoxylatePEI 600 E20 Diethylenetriamine 0.9 1 Pentaacetic Acid Dequest 2010 1.5 11.1 Optical brightening agent 1 1.2 2.5 0.5 0.2 MgCl₂ 0.7 0.2 Potassiumsulfite 0.5 0.35 0.2 Structurant 0.21 0.13 0.15 Silicone softening agent2.5 (PDMS) Water 8 10 7 6 9 Miscellaneous (dyes, To 100 To 100 To 100 To100 To 100 aesthetics, perfume etc) Monoethanol amine To pH To pH 7.5 TopH 7.4 To pH 7.6 To pH 7.6 To pH 7.6 7.6 ¹Preferred LAS also comprise analkyl group comprising from about 9 to about 15 carbon atoms, instraight chain configuration.

The detergents can include the formulation presented in Table 9.

TABLE 9 N Wt. % Dimethyl monoethyl ether 73.87 Sodium lauryl sulfate6.00 Dimethyl glyoxime 1.00 Isopropyl alcohol 0.5 Triazine stilbene(Tinopal UNPA-GX) 0.4 Monoethanol amine 1.52 Linear alcohol ethoxylate(Surfonic LF-17) 13.61 d-limonene 3.00

The composition can include the formulation presented in Table 10.

TABLE 10 O P Wt. % Wt. % Cationic Softener Active¹ 65.0 65.0 Fatty Acid²1.8 1.8 TMPD³ 14.7 14.7 Cocoamide 6EO⁴ 4.05 4.05 Perfume 5 2.5 PerfumeMicrocapsules — 1.25 Dye 0.001 0.001 Hexylene Glycol⁶ 5.63 5.6 Ethanol⁶5.63 5.6 ¹Di(acyloxyethyl)(2-hydroxy ethyl) methyl ammonium methylsulfate wherein the acyl group is derived from partially hydrogenatedcanola fatty acid. ²Partially hydrogenated canola fatty acid.³2,2,4-trimethyl-1,3-pentanediol ⁴PEG 6 cocamide - polyethylene glycolamide of coconut fatty acid. ⁵ Sodium salt of hydroxyethane diphosphonicacid ⁶Material included with softening active by supplier.

Multi-compartment pouches can contain a plurality of benefit agents. Byway of a non-limiting example, a two- or three-component pouch maycontain the formulations presented in Table 11 in separate enclosures,where dosage is the amount of the formulation in the respectiveenclosure.

TABLE 11 Q R S 3 compartments 2 compartments 3 compartments Compartment# 1 2 3 1 2 1 2 3 Dosage (g) 34.0 3.5 3.5 30.0 5.0 25.0 1.5 4.0Ingredients Weight % Alkylbenzene sulfonic acid 20.0 20.0 20.0 10.0 20.020.0 Alkyl sulfate 2.0 C12-14 alkyl 7-ethoxylate 17.0 17.0 17.0 17.017.0 Cationic surfactant 1.0 Zeolite A 10.0 C12-18 Fatty acid 13.0 13.013.0 18.0 18.0 Sodium acetate 4.0 enzymes 0-3 0-3 0-3 0-3 0-3 SodiumPercarbonate 11.0 TAED 4.0 Organic catalyst¹ 1.0 PAP granule² 50Polycarboxylate 1.0 Polyethyleneimine ethoxylate³ 2.2 2.2 2.2Hydroxyethane diphosphonic acid 0.6 0.6 0.6 0.5 Ethylene diaminetetra(methylene 0.4 phosphonic) acid Brightener 0.2 0.2 0.2 0.3 0.3Mineral oil Hueing dye⁴ 0.05 0.035 0.12 Perfume 1.7 1.7 0.6 1.5 Waterand minors (antioxidant, 10.0 10.0 10.0 4.0 aesthetics, . . . ) Buffers(sodium To pH 8.0 for liquids carbonate, monoethanolamine)⁵ To RA > 5.0for powders Solvents (1,2 propanediol, ethanol) To 100% for liquids,sodium sulfate for powders ¹Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-ethyl-hexyloxymethyl)-ethyl]esteras described in U.S. Pat. No. 7,169,744 ²PAP =Phtaloyl-Amino-Peroxycaproic acid, as a 70% active wet cake³Polyethylenimine (MW = 600) with 20 ethoxylate groups per —NH.⁴Ethoxylated thiophene, EO (R₁ + R₂) = 5 ⁵RA = Reserve Alkalinity (gNaOH/dose)In another embodiment of multicomponent pouches, the respectiveenclosures can be filled with liquid and solid benefit agents.Non-limiting examples of two compartment pouches, where one enclosure isfilled with a liquid and one is filled with a solid, includecombinations of the formulations presented in Tables 12 and 13.

TABLE 12 T U V W Liquid formulation XL1 XL2 XL3 XL4 dosage 10 g 5 g 15 g7 Wt % Wt % Wt % Wt % Marlipal C24-7 74 20 14 Non ionic surfactantNeodol 23-5 55 Anionic surfactant¹ 20 20 25 Propane diol 10 4 22 10Glycerol 2 5 5 Soil dispersant² 2 Amphiphilic alkoxylated grease 5cleaning polymer³ Fatty acid 10 20 Enzymes 3 Structurant 3 Perfume 7 10Water 2 3 5 Monoethanol amine To pH 7.5 Minors To 100% ¹Linear C11-13alkyl benzene sulfonic acid²(bis(C₂H₅O)(C₂H₄O)_(n))(CH₃)—N⁺—CxH2x—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)_(n)),wherein n = from 15 to 30, and x = from 3 to 8.Random graft copolymer is a polyvinyl acetate grafted polyethylene oxidecopolymer having a polyethylene oxide backbone and multiple polyvinylacetate side chains. The molecular weight of the polyethylene oxidebackbone is about 6000 and the weight ratio of the polyethylene oxide topolyvinyl acetate is about 40 to 60 and no more than 1 grafting pointper 50 ethylene oxide units.

TABLE 13 X Y Z AA Powder formulation XP1 XP2 XP3 XP4 Dosage 35 g 25 g 40g 30 g Wt % Wt % Wt % Wt % Anionic surfactant 20 20 20 Cationicsurfactant 1.5 1.5 Bleach agent 20 36 36 36 Chelating agent 0.8 2 2 2Enzyme 10 10 10 Sodium carbonate 6 4 4 Sodium bicarbonate 4 4 Zeolite 4020 15 15 Fluorescent whitening agent 0.5 3 1 Polymers 2 5 5 Sodiumsulfate 15 Minors To 100%

A hard surface cleaning composition, which may be used by professionals,can include the formulation presented in Table 14.

TABLE 14 Ingredient Name WT % C10 alkyl alcohol-8-ethoxylate 55.0 Linearalkylbenzene sulfonic acid 9.0 Monoethanolamine 2.4 1,2 propanediol 9.0Glycerol 7.5 C1218 alkyl fatty acid 2.5 Dye 0.1 Perfume 2.2 WaterBalance

The foregoing description is given for clearness of understanding only,and no unnecessary limitations should be understood therefrom, asmodifications within the scope of the invention may be apparent to thosehaving ordinary skill in the art.

Throughout this specification and the claims which follow, unless thecontext requires otherwise, the word “comprise” and variations such as“comprises” and “comprising” will be understood to imply the inclusionof a stated integer or step or group of integers or steps but not theexclusion of any other integer or step or group of integers or steps.

Throughout the specification, where compositions are described asincluding components or materials, it is contemplated that thecompositions can also consist essentially of, or consist of, anycombination of the recited components or materials, unless describedotherwise. Likewise, where methods are described as including particularsteps, it is contemplated that the methods can also consist essentiallyof, or consist of, any combination of the recited steps, unlessdescribed otherwise. The invention illustratively disclosed hereinsuitably may be practiced in the absence of any element or step which isnot specifically disclosed herein.

The practice of a method disclosed herein, and individual steps thereof,can be performed manually and/or with the aid of or automation providedby electronic equipment. Although processes have been described withreference to particular embodiments, a person of ordinary skill in theart will readily appreciate that other ways of performing the actsassociated with the methods may be used. For example, the order ofvarious of the steps may be changed without departing from the scope orspirit of the method, unless described otherwise. In addition, some ofthe individual steps can be combined, omitted, or further subdividedinto additional steps.

All patents, publications and references cited herein are hereby fullyincorporated by reference. In case of conflict between the presentdisclosure and incorporated patents, publications and references, thepresent disclosure should control.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to the term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. An article comprising: a. a water-soluble film, wherein thewater-soluble film comprises: a polyvinyl alcohol (PVOH) polymer, thePVOH polymer comprising a PVOH homopolymer that includes vinyl alcoholmonomer units and optionally vinyl acetate monomer units; dipropyleneglycol as a first plasticizer; a sugar alcohol as a second plasticizer,wherein the sugar alcohol is selected from the group consisting ofisomalt, maltitol, sorbitol, xylitol, erythritol, adonitol, dulcitol,pentaerythritol, and mannitol; and a polyol as a third plasticizer, thethird plasticizer being selected from the group consisting of glycerin,diglycerin, ethylene glycol, diethylene glycol, triethyleneglycol,tetraethylene glycol, polyethylene glycols up to 400 MW, neopentylglycol, propylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane,and polyether polyols; and b. a household care composition. 2.(canceled)
 3. The article of claim 1, wherein the sugar alcohol issorbitol.
 4. (canceled)
 5. The article of claim 1, wherein the polyol isglycerin.
 6. The article of claim 1, wherein the water-soluble filmcomprises: the polyvinyl alcohol (PVOH) polymer; dipropylene glycol asthe first plasticizer; sorbitol as the second plasticizer; and glycerinas the third plasticizer; wherein the first, second, and thirdplasticizers are present in the water-soluble film in a combined amountin a range of about 5 parts to about 50 parts total plasticizer per 100parts total resin (phr) in the water-soluble film.
 7. The article ofclaim 1, wherein the first, second, and third plasticizers are presentin the water-soluble film in a combined amount in a range of about 5parts to about 40 parts total plasticizer per 100 parts total resin(phr) in the water-soluble film.
 8. The article of claim 1, wherein: thewater-soluble film has an aged tensile strength of at least about 25 MPaas measured by the Aged Tensile Strength Test; and the water-solublefilm has a seal tear value of at least about 170% as measured by the SumSeal Tear Test.
 9. The article of claim 1, wherein: the firstplasticizer is present in the water-soluble film in an amount in a rangeof about 10 wt. % to about 40 wt. % relative to the combined amount ofthe first, second, and third plasticizers in the water-soluble film; thesecond plasticizer is present in the water-soluble film in an amount ina range of about 10 wt. % to about 30 wt. % relative to the combinedamount of the first, second, and third plasticizers in the water-solublefilm; and the third plasticizer is present in the water-soluble film inan amount in a range of about 40 wt. % to about 70 wt. % relative to thecombined amount of the first, second, and third plasticizers in thewater-soluble film.
 10. The article of claim 1, wherein: the firstplasticizer is present in the water-soluble film in an amount in a rangeof about 10 wt. % to about 65 wt. % relative to the combined amount ofthe first, second, and third plasticizers in the water-soluble film. 11.The article of claim 1, wherein: the second plasticizer is present inthe water-soluble film in an amount in a range of about 10 wt. % toabout 65 wt. % relative to the combined amount of the first, second, andthird plasticizers in the water-soluble film.
 12. The article of claim1, wherein: the third plasticizer is present in the water-soluble filmin an amount in a range of about 25 wt. % to about 80 wt. % relative tothe combined amount of the first, second, and third plasticizers in thewater-soluble film.
 13. The article of claim 1, wherein: the firstplasticizer is present in the water-soluble film in an amount in a rangeof about 13 wt. % to about 58 wt. % relative to the combined amount ofthe first, second, and third plasticizers in the water-soluble film; thesecond plasticizer is present in the water-soluble film in an amount ina range of about 13 wt. % to about 58 wt. % relative to the combinedamount of the first, second, and third plasticizers in the water-solublefilm; and the third plasticizer is present in the water-soluble film inan amount in a range of about 28 wt. % to about 73 wt. % relative to thecombined amount of the first, second, and third plasticizers in thewater-soluble film.
 14. The article of claim 1, wherein: the firstplasticizer is present in the water-soluble film in an amount in a rangeof about 13 wt. % to about 19 wt. % relative to the combined amount ofthe first, second, and third plasticizers in the water-soluble film; thesecond plasticizer is present in the water-soluble film in an amount ina range of about 41 wt. % to about 52 wt. % relative to the combinedamount of the first, second, and third plasticizers in the water-solublefilm; and the third plasticizer is present in the water-soluble film inan amount in a range of about 35 wt. % to about 44 wt. % relative to thecombined amount of the first, second, and third plasticizers in thewater-soluble film.
 15. The article of claim 1, wherein thewater-soluble film has at least two of the three properties (a), (b),and (c): (a) an aged melting transition delta elevation of about 12° C.or less as measured by the Aged Melting Transition Delta Test; (b) anaged adhesion value of at least about 1300 g/s as measured by the AgedAdhesion Test; and (c) an aged tensile strength of at least about 25 MPaas measured by the Aged Tensile Strength Test.
 16. The article of claim1, wherein the water-soluble film further comprises one or morecomponents selected from the group consisting of plasticizers other thanthe first, second, and third plasticizers, plasticizer compatibilizers,lubricants, release agents, fillers, extenders, cross-linking agents,antiblocking agents, antioxidants, detackifying agents, antifoams,nanoparticles, bleaching agents, surfactants, and combinations thereof.17. The article of claim 1, wherein the PVOH polymer further comprises aPVOH copolymer comprising an anionic monomer unit, a vinyl alcoholmonomer unit, and optionally a vinyl acetate monomer unit.
 18. Thearticle of claim 17, wherein the anionic monomer is selected from thegroup consisting of vinyl acetic acid, maleic acid, monoalkyl maleate,dialkyl maleate, monomethyl maleate, dimethyl maleate, maleicanyhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate,monomethyl fumarate, dimethyl fumarate, fumaric anyhydride, itaconicacid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride,vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid,2-acrylamido-1-methylpropanesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts of the foregoing, esters of the foregoing, andcombinations thereof.
 19. The article of claim 1, wherein the PVOHpolymer comprises a polymer blend comprising two or more different PVOHhomopolymers.
 20. (canceled)
 21. (canceled)
 22. The article of claim 1,wherein the article is in the form of a pouch comprising at least onesealed compartment.
 23. The article of claim 22, wherein the at leastone compartment comprises at least one wall, wherein the at least onewall comprises the water-soluble film.
 24. The article of claim 22,wherein the pouch comprises at least two compartments.
 25. The articleof claim 24, wherein a second compartment is superposed on a firstcompartment.
 26. The article of claim 24, wherein the pouch comprises atleast three compartments.
 27. The article of claim 22, wherein thehousehold care composition is contained in the at least one compartment.28. The article of claim 1, wherein the household care composition isselected from the group consisting of light duty liquid detergentscompositions, heavy duty liquid detergent compositions, hard surfacecleaning compositions, detergent gels commonly used for laundry,bleaching compositions, laundry additives, fabric enhancer compositions,shampoos, body washes, other personal care compositions, and mixturesthereof.
 29. The article of claim 1, wherein the household carecomposition comprises surfactant.
 30. The article of claim 1, whereinthe household care composition is in the form of a liquid, solid, apowder, or mixtures thereof.
 31. The article of claim 1, wherein thehousehold care composition is in contact with the water-soluble film.32. A method of forming the article of claim 1, wherein the methodcomprises the steps of: providing the water-soluble film, wherein thefilm defines an interior pouch container volume; filling the containervolume with a household care composition; and sealing the film to form asealed compartment, wherein the sealed compartment contains thecomposition.
 33. A method of treating a substrate, wherein the methodcomprises the step of contacting the substrate with the article ofclaim
 1. 34. The article of claim 19, wherein the polymer blendcomprises a first partially hydrolyzed PVOH homopolymer and a secondpartially hydrolyzed PVOH homopolymer in about a 50 wt. %/50 wt. %ratio.
 35. The article of claim 1, wherein the PVOH polymer comprises afirst partially hydrolyzed PVOH homopolymer that is characterized by a4% solution viscosity of about 13 cP.
 36. The article of claim 1,wherein the PVOH polymer comprises a second partially hydrolyzed PVOHhomopolymer that is characterized by a 4% solution viscosity of about 23cP.